Studies Toward the Optimization of Energy Migration
in Rigid-Rod Surfactant Polymers
by
Sean Konrad McHugh
B.S., Chemistry (1995)
University of California, Irvine
Submitted to the Department of Chemistry
in Partial Fulfillment of the Requirements for the Degree of
Master of Science in Chemistry
at the
Massachusetts Institute of Technology
February 1998
© 1998 Massachusetts Institute of Technology.
All rights reserved.
..
Signature of Author ..................................
Certifiedby ....-.
..........
.....
............. .... ..... .......
;/
•Timothy
/)
A ccepted by .........
.....
....
"
..
.........-.
Department of Chemistry
January 20, 1998
.
M. Swager
Professor of Chemistry
Thesis Supervisor
............... ......
................
Dietmar Seyferth
Chairman, Departmental Committee on Graduate Students
MAR O3'~
STUDIES TOWARD THE OPTIMIZATION OF ENERGY MIGRATION
IN RIGID-ROD SURFACTANT POLYMERS
by
Sean Konrad McHugh
Submitted to the Department of Chemistry
on January 20, 1998 in partial fulfillment of the
requirements for the Degree of Master in Science in
Chemistry
ABSTRACT
Rigid-rod p-phenyleneethynylene surfactant polymers were synthesized in an attempt to
obtain polymer alignment and possibly enhance energy migration in those polymer chains.
Two methods were investigated in this thesis to determine if alignment of the polymer chains
could be obtained. The first of these methods was through the use of the inherent anisotropy
of lyotropic liquid crystalline polymers, and the second method was through the preparation
of aligned Langmuir-Blodgett thin films. The two types of surfactant polymers that were
synthesized, ionic and non-ionic, did not yield any lyotropic liquid crystal solutions, mainly
because of the low solubility of the polymers. However, some of the non-ionic polymers did
give alignment in Langmuir-Blodgett thin films, which was measured using polarized UVVis spectroscopy. In the course of these studies, a polymer containing a pendant 15-crown-5
was determined to show particular sensitivity to potassium ions. This effect was measured
using UV-Vis and fluorescence spectroscopy. The same effect was not seen with lithium or
sodium.
Thesis Supervisor: Timothy M. Swager
Title: Professor of Chemistry
Table of Contents
Page
Abstract ..................................................................................................................
Table of Contents ..................................................................................................
List of Figures .......................................................................................................
Acknow ledgm ents ...................................................................................................
Chapter 1.
2
3
4
7
Introduction to Conjugated Polymers, Lyotropic
Liquid Crystals, and Langmuir-Blodgett Thin
Film Preparation
i. Conjugated Polymers .................................................... 9
. 10
ii. Chemical Sensor Background .....................................
..... 11
iii. Sensor Amplification ......................................
14
iv. Amplification Enhancement .....................................
Chapter 2.
Synthetic Work Toward Surfactant Polymers
i. Introduction .................................... . ...............................
ii. Palladium Coupling Reaction .....................................
iii. Results .................................... . ................
Chapter 3.
21
21
23
Results on Surfactant Polymers
i. LB Alignment of Polymers ........................................ 39
ii. Ion Sensitivity ................................................ 42
iii. Conclusions ................................................. 46
Chapter 4.
Experimental Section ........................................
Bibliography ................................................................................
Appendix ..................................................................................
..... 47
............................ 69
............................... 71
List of Figures
Chapter 1
Figure
Figure
Figure
Figure
1.1
1.2
1.3
1.4
Figure 1.5
Figure 1.6
Figure 1.7
Figure 1.8
Examples of conjugated polymers.
Coumarin dye/cryptand-based K+ sensor.
Examples of conducting polymer sensors.
p-Phenyleneethynylene polymer with cyclophane receptor that binds
paraquat.
Diagram of amplified quenching effect of paraquat on a cyclophanecontaining conjugated polymer.
A surfactant (sodium dodecylsulfate) and an illustration.
Micelle and columnar phases.
Illustration describing the LB thin film preparation technique.
Chapter 2
Figure 2.1
Figure 2.2
Figure 2.3
Figure 2.4
Figure 2.5
Examples of rigid-rod surfactant polymers.
Palladium coupling reaction catalytic cycle.
Target surfactant polymers.
Phosphonic acid surfactant polymer target.
Non-ionic surfactant polymer targets.
Chapter 3
Figure 3.1
Figure 3.2
Figure 3.3
Figure 3.4
Figure 3.5
Figure 3.6
Figure 3.7
Surfactant polymers used for LB films.
UV-Vis spectrum of 10-layer LB film of 42. The two spectrums show
the anisotropy of the polymer film.
Pressure-Area isotherm for 42 with different subphases.
Fluorescence spectra of 42 before and after the addition of potassium
salts.
UV-Vis absorption spectrum of 42 before and after addition of
potassium ions.
Crown ether interactions with alkali metals.
Possible interactions of 42 with potassium ions.
Appendix
Figure A1.1.
1H
NMR spectrum (300 MHz, CDC13 ) of compound 2.
Figure A1.2.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 2.
Figure A1.3.
1H
NMR spectrum (250 MHz, CDC13 ) of compound 3.
Figure A1.4.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 3.
Figure A1.5.
1H NMR spectrum (250 MHz, CDC13 ) of compound 4.
Figure A1.6.
13 C NMR
Figure A1.7.
1H
spectrum (125 MHz, CDC13) of compound 4.
NMR spectrum (250 MHz, CDC13 ) of compound 5.
Figure A1.8.
13 C NMR
Figure A1.9.
1H
NMR spectrum (300 MHz, CDC13 ) of compound 6.
Figure A1.10.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 6.
Figure Al.11.
1H
NMR spectrum (300 MHz, CDC13 ) of compound 8.
Figure A1.12.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 8.
Figure A1.13.
1H
NMR spectrum (300 MHz, CDC1 3 ) of compound 9.
Figure A1.14.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 9.
spectrum (125 MHz, CDC1 3 ) of compound 5.
Figure A1.15. 1H NMR spectrum (250 MHz, CDC1 3) of compound 11.
Figure A1.16.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 11.
Figure A1.17. 1H NMR spectrum (250 MHz, CDC13 ) of compound 12.
Figure A1.18.
1H
Figure A1.19.
13 C NMR
Figure A 1.20.
1H
NMR spectrum (300 MHz, CDC1 3 ) of compound 16.
Figure A1.21.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 16.
Figure A 1.22.
1H
NMR spectrum (300 MHz, CDC13 ) of compound 18.
Figure A1.23.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 18.
Figure A 1.24.
1H
NMR spectrum (250 MHz, CDC13 ) of compound 19.
Figure A1.25.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 19.
NMR spectrum (250 MHz, CDC1 3 ) of compound 15.
spectrum (125 MHz, CDC1 3 ) of compound 15.
Figure A1.26. 1H NMR spectrum (250 MHz, CDC13 ) of compound 20.
Figure A 1.27. 13 C NMR spectrum (125 MHz, CDC13) of compound 20.
Figure A1.28. 1H NMR spectrum (500 MHz, CDC13 ) of compound 21.
Figure A 1.29.
1H
NMR spectrum (300 MHz, CDC13 ) of compound 22.
Figure A1.30.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 22.
Figure A1.31.
1H
NMR spectrum (250 MHz, CDC13 ) of compound 23.
Figure A1.32.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 23.
Figure A1.33.
1H
NMR spectrum (250 MHz, CDC13 ) of compound 24.
Figure A1.34.
13 C NMR
spectrum (125 MHz, CDC13 ) of compound 24.
Figure A1.35.
tH
NMR spectrum (300 MHz, CDC13 ) of compound 25.
Figure A1.36.
13 C
NMR spectrum (125 MHz, CDC13 ) of compound 25.
Figure A1.37. 1H NMR spectrum (250 MHz, CDC13 ) of compound 26.
Figure A1.38. 1H NMR spectrum (250 MHz, CDC13 ) of compound 29.
Figure A1.39.
13
C
NMR spectrum (125 MHz, CDC13) of compound 29.
Figure A 1.40. 1H NMR spectrum (250 MHz, CDC13 ) of compound 30.
Figure A1.41. 13C NMR spectrum (125 MHz, CDC13 ) of compound 30.
Figure A1.42. 1H NMR spectrum (250 MHz, CDC13 ) of compound 31.
Figure A1.43. 13C NMR spectrum (125 MHz, CDC13 ) of compound 31.
Figure A1.44. 1H NMR spectrum (300 MHz, CDC13 ) of compound 32.
Figure A1.45.
13
C
NMR spectrum (125 MHz, CDC13 ) of compound 32.
Figure A1.46. 1H NMR spectrum (250 MHz, CDC13 ) of compound 33.
Figure A 1.47.
13C
NMR spectrum (125 MHz, CDC13 ) of compound 33.
Figure A1.48. 1H NMR spectrum (300 MHz, CDC13 ) of compound 34.
Figure A1.49. 1H NMR spectrum (250 MHz, CDC13 ) of compound 36.
Figure A1.50.
13C
NMR spectrum (125 MHz, CDC13) of compound 36.
Figure A1.51. 1H NMR spectrum (250 MHz, CDC13 ) of compound 37.
Figure A 1.52.
13C
NMR spectrum (125 MHz, CDC13 ) of compound 37.
Figure A1.53. IH NMR spectrum (250 MHz, CDC13 ) of compound 38.
Figure A 1.54.
13C
NMR spectrum (125 MHz, CDC13 ) of compound 38.
Figure A1.55. 1H NMR spectrum (300 MHz, CDC13 ) of compound 39.
Figure A 1.56. 1H NMR spectrum (300 MHz, CDC13 ) of compound 40.
Figure A1.57. 1H NMR spectrum (250 MHz, CDC13 ) of compound 41.
Figure A1.58. 1H NMR spectrum (300 MHz, CDC13 ) of compound 42.
Acknowledgments
To Professor Timothy Swager for giving me the opportunity to work in his labs and benefit
from his wealth of knowledge.
To the Swager Group members for their help, advice, and good humor.
To Jinsang Kim, for the work on the Langmuir-Blodgett thin films.
To my family, for their support.
To Beth, for all the support and love.
Chapter 1
Introduction to Conjugated Polymers, Lyotropic Liquid Crystals, and
Langmuir-Blodgett Thin Film Preparation
i. ConjugatedPolymers
Conjugated organic polymers, which are polymers that have a highly delocalized ir
system, have become increasingly important in materials research, bringing forth many new
discoveries in recent years. 1 The initial discovery that doped trans-polyacetylene(Figure
1.1) can exhibit conductivities as high as 1.5 x 105 S/cm, that of a conducting metal, led
many efforts of research in this area. 2 Initially, most of the effort was directed at trying to
overcome the setbacks of polyacetylene, which is insoluble and very sensitive to air
oxidation. Both of these attributes make polyacetylene very difficult to process for any
useful applications. In an attempt to overcome these problems, other polymers (Figure 1.1)
were developed, some of which were also highly conductive when doped. 3 Although some
of the polymers shown in Figure 1.1 are also insoluble, addition of alkyl- or alkoxy- chains to
the polymer backbone has led to soluble analogs of most of these polymers.
Polyacetylene
Polypyrrole
Ip on
Polyparaphenylene
ethynylene
H
Polythiophene
CH= CH)-
Polyparahenylene
-4
-n
\ /
n
n
Polyquinoline
Figure 1.1. Examples of conjugated polymers.
Aside from the developments in conducting polymers, research in conjugated
polymers has brought forth a number of other applications. Some of the most notable
applications discovered to date are those in electroluminescent devices (for example, LEDs)
and chemical sensors.
The first of these areas, LEDs, has recently garnered worldwide interest. The use of
The first of these areas, LEDs, has recently garnered worldwide interest. The use of
organic polymers in LEDs would bring many advantages over conventional inorganic
semiconductor technology. Some of these advantages are that organic polymers are easily
processed to form useful structures, they can be more economically feasible in large display
areas, and there are a large number of different colors available. Some of these colors were
only recently available in inorganic semiconductors. 4 ,5
Another area that has also been gaining widespread interest is the use of conjugated
polymers in chemical sensing devices. There are two main methods in which conjugated
polymers are used as chemical sensors. In the first method, the sensor is based on
conductivity changes in a conjugated polymeric material upon binding of an analyte. In the
second method, optical changes in a conjugated polymer (a change in either the absorption or
the emission wavelength of light) signal the binding of an analyte to a receptor.
ii. ChemicalSensor Background
The need for chemical sensors, whether monomeric or polymeric, is continually
growing. There have been many monomeric chemosensors developed for the detection of
ions, aromatic hydrocarbons, and sugar molecules. 6 The ability to measure "real-time"
concentrations of analytes such as K+ in a person's bloodstream during heart surgery is
extremely important. This detection can be accomplished using fluorescent receptors such as
the coumarin dye shown in Figure 1.2, which can measure intracellular K+ concentration. 7
,/rN
--- I
CH3
Figure 1.2. Coumarin dye/cryptand-based K+ sensor.
Most of the chemical sensors used today are monomeric receptors that are based on
decrease, or a wavelength shift in the absorption or emission of light. Some of the most
sensitive of these chemosensors use fluorescence as the signal, because fluorescence
spectroscopy is a very sensitive technique, and it is even possible to detect the fluorescence
of a single molecule. One main setback of this type of sensor is that high sensitivity can be
obtained only by having a very large binding constant between the receptor and the analyte.
This leads to two possible problems: First, for the detection of certain analytes, it may be
impossible to develop receptors with large binding constants, and second, a large binding
constant can produce an irreversible sensor that must somehow be "reset" to is its original
condition. These problems would require more complicated and expensive devices.
Numerous chemical sensors are commercially available at this point in time. A very
common and inexpensive one, phenolphthalein, changes color in visible light at a certain pH,
effectively making it a H+ ion sensor. However, this sensor is very limited in actual
applications. Other, more complicated mechanical sensing devices, such as catalytic
devices, 8 are used to determine the concentration of compounds by destructive methods. An
example of a catalytic device is one that uses a solid-phase catalyst to determine the
concentration of flammable gases by reacting them with oxygen:
CH4
+
02
Catalyst
A)
CO 2
+
2H 2 0
In this case, the heat of reaction is used to determine the concentration of flammable
gas present. This type of device is limited by the necessity of high temperature for the
reaction to proceed, and at this temperature, the catalyst is slowly degraded and can easily be
poisoned by reaction with compounds such as thiols. Other problems with this type of sensor
are that the reaction is irreversible and that the sensor is not specific for a single compound;
any one of a number of flammable gases would be detected.
iii. Sensor Amplification
Another way to obtain high sensitivity while circumventing the problem of
irreversibility is to the use a method that can amplify the response of a binding event. This is
where the use of conjugated polymers has become increasingly important. In this method,
the collective property of the system, either conductivity or energy migration, is used to
amplify a binding event. In the case of conductivity, any binding event on a single polymer
chain, acting essentially as a defect, can cause dramatic changes in the conductivity of the
material as a whole. 9 Some examples of polymeric systems that have been developed based
on conductivity changes are shown below (Figure 1.3).10
NH2
q
/LO
NH
0
0
0
n
Glucose Oxidase
Figure 1.3. Examples of conducting polymer sensors.
The first example that is shown, a polyazulene functionalized with glucose oxidase, is
a glucose-sensitive polymer. Reaction of the polymer-bound enzyme with glucose causes an
oxidation of the polymer, which in turn causes an increase in the conductivity. The second
example shown is a bithiophene-crown polymer that is sensitive to ionic species. Binding of
a metal ion by the crown ether causes a twisting of the polymer's backbone, which then
causes a decrease in conductivity.
In the case of energy migration amplifying the binding of an analyte, the polymer acts
as an antenna that funnels energy to the receptor that has bound an analyte. This will either
lead to a quenching of the fluorescence by this site or, if it is a local minima in the band
structure, cause a shift in the wavelength of fluorescence. As proof of this concept, Swager
has developed a conjugated polymeric system that amplifies the quenching effect upon
binding of a paraquat molecule to a cyclophane receptor built into the polymer backbone. 11
This poly(p-phenyleneethynylene), containing a diamidobenzene and a cyclophane receptor,
is shown in Figure 1.4. Also shown is an illustration of the cyclophane receptor on the rigidrod polymer.
0O O
NR2
R2N
O
O
O
^O O
go
n
O
O
R = C 8H 17
Mn = 65,000
Figure 1.4. p-Phenyleneethynylene polymer with cyclophane receptor that binds paraquat.
An illustration of the amplification of a binding event through energy migration is
shown in Figure 1.5. The excitation formed by absorption of ultraviolet light can migrate
along the polymer backbone until it encounters the paraquat molecule, which quenches the
fluorescence. The use of the polymer gives a 65-fold enhancement of quenching over a
single receptor model system. This amplification caused by the energy migration is limited,
however, by the lifetime and mobility of the excitations. Beyond a molecular weight of
-65,000, there is no further enhancement in sensitivity to paraquat.
SConduction
Band
©
\
q
hu
Valence
Band
+
5U
-U
CH3N
H3
Figure 1.5. Diagram of amplified quenching effect of paraquat on a cyclophane-containing
conjugated polymer. 11
Amplification of a chemical sensor through energy migration in a conjugated polymer
may be further enhanced by effectively extending the conjugation of the polymer. Even
though the p-phenyleneethynylene polymer is expected to have a rigid-rod backbone,
acetylene-phenyl bonds do allow for more bending of the bond than would have been
expected. This extra bending allows the polymer, which is very long, to coil up on itself and
the solvent. This is the reason that even though polymers such as the paraquat sensor
developed by Swager can be made with molecular weight higher than 65,000, the effective
length of the polymer is limited by its morphology in solution.
iv. Amplification Enhancement
There are two methods investigated in this thesis to determine if the amplification of
energy migration in rigid-rod p-phenyleneethynylene polymers could be enhanced by
aligning the polymer chains. The first of these methods was through the use of the inherent
anisotropy of lyotropic liquid crystalline polymers, and the second method was through the
preparation of aligned Langmuir-Blodgett thin films.
The first method of alignment described would make use of the inherent order of the
liquid crystalline state, which is a phase of matter between that of crystals and that of liquids.
Liquid crystals maintain some of the order found in crystalline solids, while also maintaining
the fluid properties of a liquid. Two main categories of liquid crystals are thermotropic and
lyotropic, and they can both be either monomeric or polymeric. 12 ,13 Thermotropic liquid
crystals form a liquid crystal phase, or mesophase, throughout a certain temperature range,
while lyotropics form a mesophase over a concentration range in one or multiple solvents,
which is also affected by temperature.
Lyotropic liquid crystals phases are usually formed by the dissolution of an
amphiphilic molecule in a solvent at a particular concentration range. An amphiphilic
molecule is one that contains both a polar (hydrophilic) group and a non-polar (hydrophobic)
group. A classic example of an amphiphile is a surfactant such as sodium dodecylsulfate,
shown in Figure 1.6 along with a common illustration used to describe surfactants. A round
ball is used to signify the polar group of the molecule, and a tail is used to signify the nonpolar chain of the surfactant. The surfactant shown here is an example of an anionic
surfactant. Other types of surfactants can be cationic, zwitterionic (both charges), or nonionic.
(IH2)11
CH3
Figure 1.6. A surfactant (sodium dodecylsulfate) and an illustration.
Because of the nature of the molecule, when a surfactant is dissolved in a solvent
such as water, the molecules aggregate to form supramolecular structures. One such
structure is a micelle, which is a spherical structure that has all the hydrophilic groups
pointing outward, while the hydrophilic chains are grouped together and protected from the
water on the inside. However, if the surfactant is dissolved in a nonpolar solvent, an inverted
micelle forms. As its name implies, this type of micelle is inverted, with the hydrophobic
chains pointing outward and the polar groups on the inside of the micelle. By changing the
concentration of the surfactant in solution, it is possible to form other supramolecular
structures such as the columnar and lamellar phases. Illustrations of the micelle and
columnar phases are shown in Figure 1.7.
Micelle Cross-Section
Micelle
Columnar
Figure 1.7. Micelle and columnar phases.
The most famous of all lyotropic liquid crystals, Kevlar, forms a liquid crystal phase
when dissolved in concentrated sulfuric acid. In this phase, greater orientation is obtained
such that when the polymer is extruded, the polymer chains are aligned and there is a much
greater strength to the material. So much, in fact, that Kevlar is 30 times stronger than nylon,
which is extruded from the liquid phase. 12
The orientation that is obtained in the liquid crystal phase can also be used for other
purposes. It was proposed that enhanced sensitivity in poly(p-phenyleneethynylene) sensors
could be obtained by the use of the orientation in lyotropic liquid crystals. By synthesizing
rigid-rod surfactant polymers that form lyotropic liquid crystalline phases, it was envisioned
that an orientation would be obtained that could lead to greater energy migration by an
excitation in the polymer backbone. It would also be possible to then dope a lyotropic liquid
crystalline polymer solution with a small quantity of receptor-containing polymer. This
would align with the surfactant polymers in the liquid crystal phase and gain enhanced
sensitivity.
Another method that could be used to obtain greater energy migration in pphenyleneethynylene polymers is the preparation of aligned Langmuir-Blodgett (LB) thin
films. It would be possible to use the same surfactant polymers that were prepared for
lyotropic ordering, to form these LB films. These aligned films would have the added
advantage of allowing for the preparation of solid state chemical sensing devices that could
be used in actual applications.
In the Langmuir-Blodgett thin film preparation technique 14 (Figure 1.8), a surface
active (surfactant) molecule, either monomeric or polymeric, is dissolved in a solvent and
dispersed on the surface of the subphase, which is usually water (a). The molecules are
compressed by Teflon barriers until they form a compact monolayer (b), and then by dipping
a solid substrate through the surface of the subphase, mono- or multilayers can be deposited
on the surface of the substrate (c). Depending on the surface of the substrate, either
hydrophilic or hydrophobic, the polar group of the molecule will be directly against the
substrate or pointing outward from it.
Movable barrier
1Subphase
Ii~'
~1l11111~
a) Surfactant spread on
subphase surface
b) Surfactant compressed
to a monolayer
LB trough
Substrate lowered
c) LB monolayer deposited
on hydrophobic substrate
Figure 1.8. Illustration describing the LB thin film preparation technique.
By depositing the surfactant polymers on the surface of the subphase and compressing to a
monolayer, and further, by depositing a monolayer on a substrate, alignment of the polymer
chains is obtained. The alignment of the polymers deposited on a glass slide can be
determined by measuring the order parameter. This is calculated by using the equation
below 15 and measuring the UV-Vis absorption of polarized light that is parallel or
perpendicular to the direction of dipping the solid substrate.
Optical Order Parameter
A
-
A
A
+
2A
=
As this equation shows, a perfectly ordered sample, with all the polymer chains
aligned in a single direction, would have an order parameter of one, while a sample with
completely disordered polymers would have an order parameter of zero. Order parameters
anywhere between 0 and 1 indicate an intermediate degree of polymer order.
Chapter 2
Synthetic Work Toward Surfactant Polymers
i. Introduction
In order to achieve alignment of rigid-rod phenyleneethynylene polymers through
either lyotropic liquid crystalline solutions or Langmuir-Blodgett thin films, it was necessary
for us to synthesize surfactant polymers. The two types of surfactant polymers we
investigated were ionic and non-ionic surfactant polymers. In the case of ionic surfactant
polymers, where the polar groups desired were cationic, anionic, or zwitterionic, the polar
groups were removed from the polymer backbone by a six-carbon alkyl chain. In the case of
non-ionic surfactants, the polar group was attached directly to the polymer backbone.
Examples of ionic and non-ionic surfactant polymers targets are shown in Figure 2.1.
N-----/---0 /OCH
0
n
C1 H21
3
n
C010
H21
Figure 2.1. Examples of a rigid-rod surfactant polymers.
ii. PalladiumCoupling Reaction
An integral part of the synthesis of the surfactant polymers in this research was the
Sonogashira-Hagiharal6,1 7 palladium coupling reaction used to create high molecular weight
polymers. This reaction has been previously used by the Swager group 11 to produce
polymers with a molecular weight greater than 1 x 106. The two components necessary for
this reaction are the aryl diiodide and the aryl diacetylene. It is possible to run the palladium
coupling reaction with an aryl dibromide; however, higher reaction temperature is required
and lower molecular weights are obtained.
A generic example of this reaction is shown below, where R and R' can be either the
same or different groups.
R
R
R
Pd (0), Cul
n
Toluene, DIPA
R'
R'
The reaction also requires stoichiometric amounts of diisopropylamine and catalytic
amounts of Pd(O) and Cul. It is possible to use either Pd(PPh 3 )4 or PdCl 2 (PPh 3 ) 2 as the
palladium source, but PdC12 (PPh3 ) 2 is avoided for the synthesis of polymers. PdC12 (PPh 3 ) 2
is reduced to Pd(O) by reaction with diisopropylamine, but it is also possible to reduce the
palladium by reductive coupling of two copper acetylide groups (formed during the reaction).
This produces a diacetylene, which affects the desired molecular weight of the polymer due
to a stoichiometry imbalance.
R
RI
Pd(O)
(a)
(d)
R-Pd(II)
R-Pd(II)-
I
R'
R' --
Cu
(c)
R-Pd(II)
R'
(b)
(e)
NH 2 I
2
Cul
H
R
+ (>cNH
2
Figure 2.2. Palladium coupling reaction catalytic cycle.
The catalytic cycle of the Sonogashira-Hagihara palladium coupling reaction is shown
in Figure 2.2.18 The catalytic cycle begins with the oxidative insertion of the palladium(0)
into the RI bond (a), followed by transmetallation of the copper acetylide with the newly
formed Pd(II) species (b). The Pd(II) species now contains two alkyl groups, R and R',
which can isomerize to a cis position (c) and then reductively eliminate (d) to form the new
alkyl-alkyl bond and Pd(O). The Pd(O) can now complete the catalytic cycle again.
In an another catalytic cycle that is connected with the main palladium cycle, the Cul
is catalytically regenerated. In this cycle, the copper acetylide is formed by the reaction of
diisopropylamine with the terminal acetylene, and then reaction with the Cul (e). The copper
acetylide then participates in the transmetallation described before (b), which regenerates the
Cul to participate in the cycle again.
iii. Results
In an attempt to produce soluble rigid-rod p-phenyleneethynylene surfactant polymers
that could be used in alignment studies, a series of polymers were synthesized. All of these
polymers were synthesized as regular hydrophobic polymers using the palladium catalyzed
coupling reaction (vida supra) and then, if possible, were subjected to reaction conditions
that would convert them to surfactant analogs. In most cases, however, solubility of the
polymers was low, and thus did not allow for their conversion to surfactant analogs. In initial
studies, a model polymer was synthesized that turned out to be a surfactant polymer itself,
capable of producing aligned Langmuir-Blodgett films. The synthesis of this polymer is
shown in Scheme 1.
Scheme 1
OCH3
OCH 3
+
KIO 3 ,1 2
KOH, KI
BrC10 H 2 1
OH
OCH 3
2-Butanone
A
OC 10oH 21
95%
CH 3 CO2 H, H 2 SO 4 , H 20
81%
2
OC10 H2 1
3
OCH3
40% aq. KOH (cat.)
TMSA, PdC12 (PPh 3) 2
THF, MeOH
Cul, Toluene, DIPA
62%
OC
67%
OC0 H2 1
OCH 3
1.1 eq. 3, Pd(PPh 3 )4
n
CuI, Toluene, DIPA
64%
10H 2 1
C 10
lH
210
6
The synthesis of polymer 6 begins with commercially available p-methoxyphenol in a
Williamson ether synthesis with 1-bromodecane to give the aryl ether 2 in 95% yield.
Standard iodination procedures 19 were used to iodinate the aromatic ring in the ortho
positions to give compound 3 in 81% yield. Coupling of two equivalents of
(trimethylsilyl)acetylene to diiodide 3 using palladium catalysis produced 4 (62%), which
was then converted to the terminal acetylene 5 (67%) using a catalytic amount of 40%
aqueous KOH solution in a tetrahydrofuran and methanol mixture. Coupling of terminal
acetylene 5 with diiodide 3 using tetrakis(triphenylphosphine)palladium afforded the rigidrod polymer 6. It was necessary to use an offset stoichiometry to obtain polymers of lower
molecular weight. Initial reactions using the standard 1 equivalent of diiodide to 1.03
equivalents of diacetylene gave insoluble polymers.
R =
C
H
0
H 3C, FH3
N+,
SO3
R
H3C, PH3
/N+cH 3
CloH21
O
II
/P -ONa
ONa
Figure 2.3. Target surfactant polymers.
Some surfactant polymer targets, which are similar to the model polymer synthesized,
are shown in Figure 2.3. The desired polar groups for these three molecules are the
sulfobetaine, the quaternary ammonium salt, and the phosphonic acid salt. Attempts to
synthesize these polymers were made; however, the solubility of either the precursor polymer
or the surfactant polymer itself limited the usefulness of these polymers. The synthesis of the
first surfactant, sulfobetaine polymer, 12, is shown below in Scheme 2. The synthesis begins
with p-decyloxyphenol, 7, a compound that was obtained from a research sample of a
previous member of the Swager group. 20 Williamson ether synthesis of aryl ether 8 was
Scheme 2
(CH 2 ) 6 Br
(CH 2 )6 Br
H
+ 5 Br(CH2)6Br
K 2 CO3
KI0 3,1 2
Acetone, A
72%
OC joH 2 1
CH 3CO 2H, H 2 S0
OC oH 2 1
I
*
H20
4,
64%
OC 10 H 2 1
8
9
/
Br
3
/N-NH
2
4N HC1
Et20, A
NaNO 2
59%
OC 10H21
OC 10H 21
11
Not Isolated
10
Scheme 2 continued
OCH 3
CH3
2.2 n-BuLi
2.4 Bu 3 SnCl
11, Pd(PPh3 )4
Toluene, DIPA
Cul added 24
hours later
THF, 0 °C
OC10 H 2 1
n
/
C10H 210
C10 H 21 0
5
12
S03
O"O
3
OCH 3
THF
C1 0H 210
C1 0H2 10
13
accomplished in 72% yield from the phenol, 7. Iodination of 8 using a potassium
iodate/iodine mixture in acetic acid gave the diiodide 9 in 64% yield. Unfortunately, some of
the primary alkyl bromide was converted to the alkyl iodide during the reaction, which
cannot be separated from the product. This was somewhat fortunate, though, because this
small portion of alkyl iodide reacts faster than the bromide, and the displaced iodide anion
acts catalytically in a Finkelstein reaction to speed up SN 2 reactions such as converting 9 to
10. Preparation of the tertiary amine 11 was accomplished in a one-pot, two-step
procedure. 2 1 In the first step, the alkyl halide 9 was reacted with dimethyl hydrazine to
produce the hydrazinium salt, 10, from which any starting material was removed by rinsing
the solid with copious amounts of diethyl ether. In the second step, reaction with sodium
nitrite in hydrochloric acid produced the tertiary amine 11 in 59% yield.
Synthesis of polymer 12 by standard palladium coupling procedures gave intractable
gels, presumably due to crosslinking by protonic sources. Therefore, an alternative
procedure was used, wherein the terminal acetylene 5 was deprotonated by n-butyllithium in
tetrahydrofuran, followed by reaction of the di-anion with tributyltin chloride. This
intermediate was then reacted in situ with the diiodide 11 as well as catalytic
tetrakis(triphenylphosphine)palladium, to yield the copolymer 12. Initially, the reaction did
not seem to proceed, but upon the addition of a catalytic amount of Cul the reaction
progressed rapidly. The mode of action that Cul displays is uncertain. It may associate with
the Pd-Ar-I intermediate and thereby activate it toward transmetallation or, alternatively, the
Cul may react directly with the stannous acetylide to form a cuprous acetylide, which is also
an intermediate in the standard cross-coupling procedures. Polymer 12 was then reacted with
1,3-propanesultone in tetrahydrofuran to yield the sulfobetaine surfactant polymer 13. This
polymer, however, was not soluble enough to investigate or characterize the possible liquid
crystalline properties of the material.
Although the surfactant copolymer 13 was not soluble, it was thought that preparing a
homopolymer might have better solubility because there would be a larger ratio of
hydrophilic groups relative to hydrophobic hydrocarbon sidechains. Attempts at synthesizing
a surfactant homopolymer, such as the one shown in Figure 2.1 (vida supra), were thwarted
by complications in coupling (trimethylsilyl)acetylene to the diiodobenzene monomer 11
(Scheme 3).
Scheme 3
I
OC
11
3~N
OCH
10 H 2 1
TMSA, PdC12 (PPh 3 )2
Toluene, DIPA
TMS~
OCoH2 1
TMS
14
In the reaction shown in Scheme 3, only complex, polymeric mixtures were obtained that
could not be separated by column chromatography. The exact reason why this reaction did
not work is not understood, but it was thought that attempting another route toward an aminebased surfactant polymer might prove worthwhile. In this case, the primary amine analog
would be synthesized using protecting groups, and then in a final step, the primary amine
could be converted to a quaternary ammonium surfactant by exhaustive methylation with
methyl iodide. This synthetic Scheme, using a previously synthesized intermediate, 9, is
shown in Scheme 4.
Scheme 4
Br
o"4
Phth
3
O
+
[(n-C 4 H 9 ) 3 P-(n-C 1 6H 33)]Br
KN
T
e ACuI,
Toluene, A
97%
I
O
OC 10 H 21
9
1.4 eq N 2H4
TMS
Phth
XTMS
I
TMS,
I
OC1 H 2 1
15
PdC 2 (PPh 3 ) 2
Toluene, DIPA
87%
ONH2
EtOH, A
OC loH
16
21
TMSX
NaBH 4
Isopropanol, H 2 0
OCloH 2 1 TMS
17
The primary amine would be prepared by a standard Gabriel synthesis. 2 2 However,
this did not work as simply as would have been expected. Compound 9, a primary alkyl
bromide, was alkylated by potassium phthalimide under phase transfer catalysis conditions 23
to afford the phthalimide derivative, 15, in 97% yield. Palladium catalyzed coupling of the
diiodide 9 and (trimethylsilyl)acetylene was completed before removal of the phthalimide
protecting group. By retaining the protecting group, any complications were avoided, and
compound 16 was obtained in 87% yield. Difficulties were encountered when trying to
remove the phthalimide group in the presence of the acetylene groups. Standard Gabriel
reaction conditions using a slight excess of hydrazine monohydrate in refluxing ethanol did
not cleanly give the desired product, 17. Another method using sodium borohydride
reduction, 24 followed by heating with acetic acid was attempted; however, this was not
successful in unmasking the primary amine.
Scheme 5
H
P
O-4
hth
I50
o
eq. N2 H4
I
OC10 H 21
TFAA, CH C1
2 2
EtOH, A
I
92%
OCloH 21
15
C F
N
3NH2
3
I
Pyridine
78%
18
OCloH
21
19
H
TMSA, PdC12 (PPh 3 )2
TMS-"0
NH2
10 LiOH-H2 0
Cul, Toluene, DIPA
91%
O
OCN3N
THF/MeOH/H 20
OCloH21 TMS
91%
20
OC0H21
21
It was thought that the problem with the phthalimide removal was the protected
acetylene functionality. By removing the phthalimide protecting group and then using
another more labile protecting group, it could have been possible to obtain the same desired
compound. This synthetic attempt is shown in Scheme 5. Removal of the phthalimide using
standard Gabriel conditions gave only low yields. Eventually, conditions for the phthalimide
removal were found, using 50 equivalents of hydrazine monohydrate. 25 This cleanly
produced the desired compound 18 in 92% yield. The primary amine was then protected as a
trifluoroacetamide (19) in 78% yield. The trifluoroacetamide is a very labile protecting
group and should be easily removed under basic conditions. 26 Coupling of
(trimethylsilyl)acetylene groups to 19, using standard palladium catalysis, gave 20 in 91%
yield, with no disturbance of the trifluoroacetamide. Removal of both the trifluoroacetamide
and the trimethylsilyl protecting groups was accomplished in 91% yield using 10 equivalents
of LiOH-H 2 0. However, at this point, attention was directed at synthesizing another type of
surfactant.
After failing to prepare a nitrogen-based surfactant, it was thought that it might be
possible to obtain lyotropic liquid crystallinity by synthesizing a phosphonic acid surfactant
whose properties could be controlled by changing the pH of solution. The target polymer,
shown in Figure 2.4, is similar to the previous nitrogen-based polymer in all respects except
for the different polar ionic group. In this method of synthesizing a surfactant polymer, the
ionic group is effectively protected as a phosphonate ester through the polymer synthesis, and
can then be converted to the phosphonic acid using a number of different methods. One
important requirement for this deprotection is that it be quantitative, so that all of the esters
are converted to the acid. The reaction shown in Figure 2.4, when used on monomeric
phosphonate esters, is quantitative, 27 ,2 8 so it was thought that this should be suitable for
reaction on a polymer.
0
Ot-
OjCH3
OCH
3 OCH
3
-n
C 1 oH 2 10
0o
II
-
+
-7-O
Naa
3
TMSI
CH 3CN
C loH
210
Figure 2.4. Phosphonic acid surfactant polymer target.
The completion of the synthesis of this polymer was not attained, because the
solubility of the non-ionic precursor did not allow the last reaction to be completed. The
synthesis of this polymer (Scheme 6) begins with compounds that were used in making the
previous amine-based surfactant polymer. Compound 22 was prepared under anhydrous
Michaelis-Becker reaction conditions 29 by addition of the alkyl halide 9 to the preformed
sodium dimethyl phosphite. This afforded phosphonate ester 22 in 77% yield. Compound 9
was used once again, by coupling two equivalents of (trimethylsilyl)acetylene under
palladium catalysis to give compound 23 in 96% yield. This reaction proceeded cleanly,
with no disruption of the primary alkyl halide. Compound 23 was then subjected to the same
Michaelis-Becker conditions as above, which produced phosphonate ester 24 in
Scheme 6
0
O
-ZOOCH
0V-.3 "CH 33
OP1
Br
3
NaP(O)(OCH3 ) 2
IO
I-
i
THF, 0 OC to 25 'C
r
I
OC1 oH2 1
OC0 H 21
22
77%
OCo10 H2 1
TMSA, PdC12 (PPh 3) 2
NaP(O)(OCH 3) 2
Cul, Toluene, DIPA
96%
THF, 0 oC to 25 oC
76%
O
"OCH 3
0"T"3 "OCH3
3OCH
22, Pd(PPh3) 4
KF, H 20
DMF, MeOH
OCoH
0 21 TMS
68%
OCloH
25
24
21
CuI, DIPA
Toluene, A
9OCH
3OCH3
C~ H21
CIoH 210
TMSI
CH 3CN
76% yield. The phosphonate ester was obtained with both acetylene protecting groups intact,
which were subsequently removed using potassium fluoride in dimethylformamide at room
temperature. 30 This method, which afforded the terminal acetylene 25 in 68% yield, was
used instead of the standard hydroxide deprotection, so that no hydrolysis of the phosphonate
ester would occur. The pendant phosphonate ester containing polymer, 26, was initially
synthesized using standard polymerization conditions between diiode 22 and diacetylene 25,
but this yielded insoluble polymers after precipitation. By using an offset stoichiometry, only
low molecular weight polymers were obtained, which would not precipitate in methanol.
Thus far, attempts at synthesizing an ionic surfactant polymer had not produced any
results, so it was thought that it might be advantageous to focus attention on non-ionic
surfactants. The polar group that would be used in this type of surfactant was an ethylene
glycol group. The two types of interest would be a triethylene glycol monomethyl ether and
a crown ether. It was hoped that the polar ethylene glycol portion of the molecule might give
added solubility, and also, in the case of the 15-crown-5, that the liquid crystalline phases
might be induced by addition of various salts. Additionally, by synthesizing polymers using
different monomers, the triethylene glycol and the 15-crown-5, it was possible to develop a
library of non-ionic surfactant polymers. The polymers that were synthesized are shown in
Figure 2.5.
00
0
0
0
OCH 3
C IH
0 2 10
CloH 210
ro
0
C 10H 210
C 10H210
0
0
OCH 3
OCH 3
Co1 H210
0
C 10H210
Figure 2.5. Non-ionic surfactant polymer targets.
As in the previous cases with ionic polymers, the solubility of some of these nonionic polymers was too low to be useful. However, in a few cases, it was possible to adjust
the reaction stoichiometry, thereby producing soluble, lower molecular weight polymers.
Studies with these nonionic surfactant polymers did not produce any lyotropic liquid
crystalline phases, but during these studies an interesting ionic sensitivity based on changes
in fluorescence was discovered. This effect was particular to the 15-crown-5/methoxy
copolymer. The syntheses of these polymers are shown in Scheme 7.
Scheme 7
"
HO
""
O
"
O
OCH 3
28
TsC1, cat. DMAP
Et 3N, CH 2C12 TsO
0 'C -> 25 'C
O"OCH3
O
29
87 %
CH 3
I
TMSI
I
CH 2C12
I
OCl 0H21 46%
3
TMS
0
O
29, K 2CO 3, cat. KI
TMSA, PdC12 (PPh3 )2
Acetone, 75 'C
J
OC 1oH2 1
I
90%
OC loH
30
O
0O
MeOH
90%
O
0
O
O
OCH 3
31, Pd(PPh 3)4, CuI
TBAF
OCloH2 1 TMS
32
CuI, Toluene, DIPA
86 %
31
OCH 3
N
21
OCo
1 H 21
Toluene, DIPA
90%
33
OCH 3
-n
Cl 0 H 2 10
34
In the first step of the convergent synthesis, commercially available triethylene glycol
monomethylether, 28, was converted to the tosylate derivative 29 in 87% yield using tosyl
chloride, triethylamine, and a catalytic amount of 4-dimethylaminopyridine (DMAP).
Selective removal of the methyl ether of compound 3 using one equivalent trimethylsilyl
iodide produced phenol 30 in 46% yield based on recovered starting material. Reaction of
the phenol, 30, under standard Williamson ether conditions with tosylate 29 produced the
triethylene glycol ether, 31, in 90% yield. Palladium catalyzed coupling between diiodide 31
and two equivalents of (trimethylsilyl)acetylene gave compound 32 in 86% yield.
Deprotection of acetylene 32 to produce terminal acetylene, 33, was accomplished in 90%
yield using tetrabutylammonium fluoride (TBAF) in methanol. Initially, the synthesis of
polymer 34 was completed using standard palladium coupling conditions; however, this
resulted in only partially soluble polymers. After changing reaction conditions to a different
monomer stoichiometry, lower molecular weight polymers were obtained.
Synthesis of the pendant 15-crown-5 homopolymer, 40 (Scheme 8), was
accomplished in a synthetic strategy very similar to the one in Scheme 7. The synthesis
begins by preparing tosylate 36 from commercially available 2-hydroxymethyl 15-crown-5,
35, in 61% yield. A lower yield was obtained than that of the corresponding tosylation in
Scheme 7 because of difficulty in isolating the product. The 15-crown-5 has a high affinity
for the ions found in the silica gel used for column chromatography, which makes separation
difficult. Williamson ether synthesis between the tosylate, 36, and phenol 30 gave compound
37 in 92% yield. Purification of this compound is easier than the crown, 36, because of the
larger ratio of non-polar to polar groups on the molecule. Coupling of the diiodide, 37, with
two equivalents of (trimethylsilyl)acetylene gave 38 in 82% yield. Removal of the
trimethylsilyl protecting groups to give the terminal acetylene, 39, was done in 87% yield
using tetrabutylammonium fluoride. This method of deprotection was used rather than KF or
KOH, because the alkali metals might get complexed between two crown ether molecules.
However, compound 33 was unstable, and after long periods at room temperature (even
under vacuum), it decomposed from a clear oil to a red one. It is possible that some metal
Scheme 8
r0
HO
3
TsCI, cat. DMAP
Et 3N, CH 2C12
61%
35
OO
OH
OC loH21
36, K 2CO 3 ,cat KI
TMSA, PdC12 (PPh3 )2
Acetone, 70 'C
92%
CuI, Toluene, DIPA
82%
OCloH 21
37
30
O0
TBAF
37, Pd(PPh3 )4, CuI
MeOH
Toluene, DIPA
47%
87 %
40
C10H2 10
OCoH21
39
0
40
ions from one of the previous reactions were trapped within the crown ethers and caused
unwanted reactions to occur. Polymerization of diiodide 37 and diacetylene 39 under
palladium catalysis gave polymer 40 in 47% yield. This low yield reflects the fact that the
reaction produced only low molecular weight oligomers. This may have been because the
diacetylene, 39, was not used right after purification, and was somewhat decomposed.
The syntheses of two other non-ionic surfactant polymers are shown in Scheme 9 and
Scheme 10. The monomers used to synthesize these polymers are from previous schemes,
and they have just been combined to form different polymers. The first of these, polymer 41,
was synthesized by reaction of the pendant crown/diiodo benzene, 31, with the pendant
triethylene glycol/diethynyl benzene 27. The reaction was done using standard palladium
coupling stoichiometries to produce polymer 41 in 80% yield. Once precipitated, however,
this polymer was not soluble.
Scheme 9
0
0
H
Pd(PPh 3 )4 , CuI
+I
Toluene, DIPA
OCloH
OC1 0 H 2 1
21
33
37
O0
CloH210
80%
0
O
OCH
C 10 H 210
41
As shown in Scheme 10, by combining the pendant crown ether/diiodo benzene
monomer, 31, with the diacetylene, 5, it was possible to synthesize copolymer 42 in 89%
yield. The synthesis of this polymer was accomplished using an offset stoichiometry so that
the reaction would yield lower molecular weight polymers that were soluble. After
synthesizing polymer 42, studies to determine if the polymer was a liquid crystal were
completed. At this time, it was discovered that 42 had an unusual fluorescence sensitivity to
potassium ions. This was not the case with lithium or sodium ions. Also, this was the only
polymer out of the non-ionic surfactant polymers that had any significant sensitivity to alkali
metals.
Scheme 10
,Q
Pd(PPh 3)4 , CuI
Toluene, DIPA
89%
37
C lOH
210
5
CloH 210
42
Chapter 3
Results on Surfactant Polymers
i. LB Alignment of Polymers
Even though some of the polymers prepared were not fully soluble, or perhaps were
intended for other purposes, it was possible to use them for the preparation of LangmuirBlodgett thin films. In the case of a polymer that was not fully soluble, the solution of the
polymer was filtered, and the soluble portion was used to make LB films. Although in some
cases this did not allow the Area/Repeat Unit of the polymer to be calculated exactly, it did
not affect the actual formation of the LB film. These films, made on glass slides, could then
be used for characterization. The different polymers that were used for LB film preparation
are shown below.
OIp OCH3
OCH 3
3 OCH 3
/
n
II
CloH 2 10
CiOH 2 1 0
19
6
0
C10 H210
0
C10H210
42
Figure 3.1. Surfactant polymers used for LB films.
LB films of the three polymers shown in Figure 3.1 were made on glass slides so that
the Order Parameter, OP, could be measured using UV-Vis spectroscopy. 3 1 The films were
made by depositing a small portion of a 1mg/mL chloroform solution of the polymer on the
surface of the subphase (water), compressing the Teflon barriers to form a monolayer of the
polymer on the surface, and then dipping a glass slide through the polymer on the surface.
For UV-Vis studies, the LB film was deposited in either a monolayer or 10 layers on a
hydrophobic glass slide that had been treated with hexamethyldisilazane. The transfer ratio,
which is the percentage of polymer out of 100% possible that was transferred to the solid
substrate, was then calculated by the software provided by Nima Technology Ltd.
Examples of the UV-Vis spectra obtained from a 10-layer sample are shown in Figure
3.2. These LB films were prepared from polymer 42 on the LB trough with pure water as the
subphase. In these spectra, the anisotropy of the LB film can be seen by the different
absorbances of the film, where the dipping direction of the substrate is either parallel or
perpendicular to the plane of polarized light used in the UV-Vis spectrum. In this case, as in
all the others, the parallel direction has a greater absorbance than the perpendicular direction,
which shows that there is a greater ordering of the polymers in the direction parallel to
dipping. The order parameter, which depends on the number of layers deposited, is
calculated using the absorbance at Xmax of these two spectra.
0.8
0.7
Parallel
_
Perpendicular
0.6
0.5
0.4
0.3
0.2
0.1
320
360
400 440 480 520
Wavelength (nm)
560
600
Figure 3.2. UV-Vis spectrum of 10-layer LB film of 42. The two spectrums show the
anisotropy of the polymer film.
A table containing the various polymers and their order parameters is shown below
(Table 3.1). As can be seen in this table, there is a small, but definite, anisotropy in the LB
films. In the case of polymer 19, the order parameter for the ten-layer film is not available,
because of problems in making an LB film with more than one layer. When trying to add
more than one layer to the LB film, the downward dip of the glass slide would transfer the
polymer as usual. However, upon removal from the subphase, the transfer ratio (amount
added to LB film) was actually negative, indicating a loss of polymer from the LB film.
Polymer
(OP) 1 Layer
(OP) 10 Layers
6
0.26
0.18
19
0.27
n/a
42
0.25
0.32
Table 3.1. Order parameters of single-layer and 10-layer LB films.
The polymer that shows the greatest ordering is 42. This polymer is interesting not
only because it is a non-ionic surfactant polymer, but because addition of alkali metals to a
solution of the polymer can cause the crown ether in the polymer to bind the metal ions,
making it an ionic surfactant polymer. Because of this interesting property, an experiment to
measure the Area/Repeat Unit of the polymer with varying alkali metals in the water
subphase was completed. A plot showing the pressure-area isotherm of 42 with different
subphases is shown in Figure 3.3. In this experiment, the subphases used were pure water,
1M KC1, and 1M NaCI.
50
-
40 --
"
-
-1MNaC1
-
----- 1M KCl
\
30
S20
10-
0
30
40
50
60
Area/Repeat Unit
70
80
90
(A2)
Figure 3.3. Pressure-Area isotherm for 42 with different subphases.
From this plot, it can be seen that there is a slight difference in the Area/Repeat Unit
of 42 with the different subphases. The Area/Repeat Unit is determined by extrapolating a
line from steepest part of the curve to the baseline, and the number at the baseline should be
the Area/Repeat Unit. The largest Area/Repeat unit, 74 A2, is found when using 1M NaCl as
the subphase. The other two subphases used, pure water and IM KC1, give similar
Area/Repeat units, both of which are smaller than the one found when using 1M NaC1. It
was not possible to form LB films with the salt solutions as subphases, because as the
substrate was removed from the subphase, a large amount of salt was left on the surface.
ii. Ion Sensitivity
With the same polymer, 42, another interesting phenomenon was discovered. There is a
significant change in the fluorescence spectrum of 42 upon addition of potassium ions (0.2M
KPF 6 in CH 3 CN) to the polymer solution. Interestingly, there is no significant change when
lithium or sodium ions are added to the solution of 42. The exact nature of this interaction is
unknown as of yet, but it can be inferred that there is some interaction of the pendant 15crown-5 species with the potassium ions. In another interesting note, the homopolymer of
the pendant 15-crown-5, 40, does not show any significant effects upon addition of potassium
or sodium ions to the solution.
[K] = 0 M to 2.0 x 1033 M
in increments of 2.0 x 10-4 M
0
440
460
480
500 520 540 560
Wavelength (nm)
580
600
Figure 3.4. Fluorescence spectra of 42 before and after the addition of potassium salts.
The fluorescence spectra of 42, including the initial pure polymer solution and those
after addition of potassium ions, are shown in Figure 3.4. Addition of a 3 gL aliquot of 0.2M
KPF6 in CH 3 CN, causes the ,max at 473 nm to decrease and split into two peaks at 480 nm
and 490 nm. Further addition of potassium causes the growth of a new maximum at 490 nm.
Both of these are shown by the arrows in the figure.
The UV-Vis absorption spectrum of 42 is shown in Figure 3.5. The two spectra
shown are the pure polymer solution and that after addition of 30 gL of a 0.2M KPF6
solution in CH 3 CN. The addition of the potassium ions caused a 10 nm red shift in the
absorbance.
0.25
0.2
0.15
O0.1
350
400
450
Wavelength (nm)
550
Figure 3.5 UV-Vis absorption spectrum of 42 before and after addition of potassium ions.
In trying to determine the nature of the effect that the potassium ion has on the
fluorescence of polymer 42, it is useful to understand the interaction between crown ethers
and alkali metals. In particular, 15-crown-5, which is contained in both polymers 40 and 42,
binds both sodium and potassium. Sodium is the correct size to fit directly inside the 15crown-5, in a 1:1 ligand to ion ratio. Potassium, which is bigger, must sit in between two 15crown-5 molecules to be bound. Examples of these effects are shown in the top of Figure
3.5. Another binding mode, which may be applicable to polymer 42, is that between a lariat
crown ether and an alkali metal. This is shown in the bottom of Figure 3.6, where an extra
arm extends above the crown, creating an additional binding site. Potassium, which likes
o
0
0
+
o
Na'
(ii )
' ~O
ox 0.o
O
0
+
O
o
K
+
O
/----k
O
O
4-0,0,,O0
--
/
O
-- _-Crown+
Figure
3.6.
Figure 3.6. Crown ether interactions with alkali metals.
to bind to six or seven oxygens, 32 can make use of the lariat shown in Figure 3.6 or a 15crown-5 with a lariat arm. Two possibilities of potassium binding to polymer 42 are shown
in Figure 3.7. In the first possibility, the potassium ion is bound between the proximate
methoxy- and 15-crown-5 in essentially a lariat crown ether. This would most likely affect
the twisting of the polymer backbone, which would in turn affect the fluorescence. In the
second possibility, the potassium ion is complexed between two crown ethers on different
molecules, which would bring the polymer chains closer to each other and allow for cofacial
nt interactions between two different polymer chains.
Sn
C10 H2
Conjugation is
enhanced when ion
is bound
C10 H21
00-
-
n
Possible ic stacking
interaction
Figure 3.7. Possible interactions of 42 with potassium ions.
iii. Conclusions
The syntheses of both ionic and non-ionic surfactant polymers have been described.
Surfactant polymers that form liquid crystalline phases were not obtained, most likely due to
solubility problems. Although the research done in this thesis was limited by the solubility of
surfactant polymers or their respective precursors, some polymers were still able to be used
for alignment in Langmuir-Blodgett thin films. Respectable order parameters were obtained
for these polymers, especially for the pendant 15-crown-5 polymer, 42. This polymer also
showed significant changes in its fluorescence spectrum upon the addition of potassium salts.
This effect was not seen with lithium or sodium, nor was it seen with the very similar
polymer 40.
Chapter 4
Experimental Section
General Methods. Air- and moisture-sensitive reactions were carried out in flame-dried
glassware using standard Schlenk-line or drybox techniques under an inert atmosphere of dry
argon. All chemicals used were of reagent grade and were purchased from Aldrich unless
otherwise noted. Anhydrous toluene was used from Aldrich Kilo-lab metal cylinders.
CH 2 C12 and THF were used directly from Aldrich Sure-seal bottles. Diisopropylamine was
distilled over solid KOH pellets and degassed by three freeze-pump-thaw cycles.
Tetrakis(triphenylphosphine)palladium (0) and trans-dichlorobis(triphenylphosphine)
palladium (II) were purchased from Strem chemicals and used as received.
(Trimethylsilyl)acetylene was purchased from Farchan Laboratories and used as received.
1H
NMR spectra were acquired on Bruker AC-250, Varian XL-300, Varian Unity 300, or
Varian VXR-500 spectrometers.
(125.66 MHz) spectrometer.
1H
13 C
and
NMR spectra were obtained on a Varian VXR 500
13 C
NMR spectra were taken in CDC13 with 1H
chemical shifts reported relative to internal tetramethylsilane (0.00 ppm) and
13 C
chemical
shifts reported relative to CDC13 (77.00 ppm). Analytical thin-layer chromatography was
performed on Merck 60 F 254 precoated silica gel plates (250 pm thickness). Flash
chromatography was performed using Lagand silica gel 60 as the stationary phase. Polymer
molecular weights were determined with a Hewlett-Packard 1100 series HPLC equipped with
a PLgel mixed-C column (5 p.) using THF as the mobile phase at a rate of 1 mL/min. Gel
permeation chromatography (GPC) measurements were made relative to mondisperse
polystyrene standards purchased from Polymer Laboratories. UV-Vis spectra were obtained
on a Hewlett-Packard 8453 diode array spectrophotometer. Fluorescence spectra of solutions
were measured at room temperature using a Spex Fluorolog spectrofluorometer. The
excitation wavelength for all spectra was 420nm. Langmuir-Blodgett (LB) thin films were
prepared on a 601M LB trough from NIMA Technology, Ltd., using purified water from a
Barnstead Nanopure system.
p-Decyloxyanisole (2). A IL, three-necked round bottomed flask equipped with a stir bar
and a condenser was charged with p-methoxyphenol (1) (32.98 g, 0.27 mol, 0.98 eq), 1bromodecane (56.25 mL, 0.27 mol, I eq.), potassium hydroxide (30.79 g, 0.55 mol, 2 eq.),
potassium iodide (5.86 g, 40 mmol, 0.13 eq) and 2-butanone (500 mL). The reaction mixture
was heated to reflux for 24 hours. After cooling to room temperature, the mixture was
partitioned between diethyl ether (750 mL) and water (500 mL). The organic layer was
separated, washed sequentially with saturated aqueous NH 4 Cl (2 x 500 mL) and water (500
mL), and then dried (MgSO4), and concentrated in vacuo. Recrystallization from THFMeOH afforded 2 as large white plates (68.10 g, 95%).
1H
NMR (300 MHz, CDC13 ) 8 6.83
(s, 4H), 3.89 (t, J = 6.6 Hz, 2H), 3.76 (s, 3H), 1.75 (qn, J = 6.6 Hz, 2H), 1.5-1.2 (br m, 14H),
0.88 (t, J = 6.9 Hz, 3H);
13 C
NMR (125 MHz, CDC13) 8 153.83, 153.50, 115.57, 114.76,
68.81, 55.85, 32.11, 29.81, 29.78, 29.64, 29.61, 29.54, 26.28, 22.89, 14.31.
2,5-Diiodo-4-decyloxyanisole (3). A 3L, three-necked round bottomed flask equipped with
a stir bar and a condenser was charged with p-decyloxyanisole (2) (30.79 g, 0.12 mol, 1 eq.),
potassium iodate (10.00 g, 50 mmol, 0.41 eq.), and iodine (32.60 g, 0.13 mol, 1.11 eq.).
Glacial acetic acid (1200 mL), conc. sulfuric acid (12 mL), and water (120mL) were added,
and the mixture heated to reflux for two days. After cooling to room temperature, the excess
iodine was quenched with 10% aqueous Na2S204 (500 mL). The resulting mixture was
further diluted with water (500 mL), filtered, and the solid dissolved in CH 2 C12 (750 mL).
The organic layer was washed sequentially with 10% aqueous Na2S204 (100 mL) and
saturated aqueous NaCl (100 mL), and then dried (MgSO4), and concentrated in vacuo .
Recrystallization in CH 2 Cl 2 -MeOH afforded 3 (48.60 g, 81%) as white needles.
1H NMR
(250 MHz, CDCl 3 ) 8 7.19 (s, 1H), 7.18 (s, 1H), 3.93 (t, J = 6.4 Hz, 2H), 3.82 (s, 3H), 1.80
(qn, J = 8.1 Hz, 2H), 1.55-1.20 (br m, 14H), 0.88 (t, J = 6.3 Hz, 3H);
13 C NMR
(125 MHz,
CDC13) 5 153.17, 152.92, 122.88, 121.44, 86.34, 85.41, 70.34, 57.13, 31.86, 29.51, 29.50,
29.28, 29.24, 29.11, 25.99, 22.65, 14.09.
2,5-Bis-((trimethylsilyl)ethynyl)-4-decyloxyanisole
(4). A 250 mL Schlenk flask equipped
with a stir bar was charged with 2,5-diiodo-4-decyloxyanisole (3) (20.00 g, 40 mmol, I eq.),
trans-dichlorobis(triphenylphosphine)palladium (II) (0.82 g, 1.20 mmol, 0.03 eq.), and
copper(I)iodide (0.46 g, 2.4 mmol, 0.06 eq.). The flask was placed under argon, and then
toluene (250 mL) and diisopropylamine (14.0 mL, 0.10 mol, 2.5 eq.) were successively
added by syringe. The deep-red solution was treated with (trimethylsilyl)acetylene (13.0 mL,
90 mmol, 2.2 eq.), and stirred for 48 hours at room temperature. The black mixture was
concentrated in vacuo, and the residue dissolved in hexanes. The hexanes solution was
filtered through a one inch plug of silica gel and eluted with chloroform. The solvent from
the filtrate was once again evaporated and the resulting solid recrystallized (methanol) to
afford 4 as yellow needles (11.05 g, 62%).
1H
NMR (250 MHz, CDCl 3) 8 6.91 (s, 1H), 6.89
(s, 1H), 3.95 (t, J= 6.3 Hz, 2H), 3.83 (s, 3H), 1.79 (qn, J= 8.2 Hz, 2H), 1.50-1.15 (br m,
14H), 0.88 (t, J= 6.9 Hz, 3H), 0.27 (s, 18H);
13 C
NMR (125 MHz, CDC13) 8 154.14, 154.07,
117.83, 113.39, 101.01, 100.90, 100.18, 100.15, 69.49, 56.36, 31.86, 29.61, 29.56, 29.40,
29.35, 29.30, 26.00, 22.65, 14.07, -0.02, -0.07.
2,5-Diethynyl-4-decyloxyanisole
(5). A 250 mL round bottomed flask equipped with a stir
bar was charged with 2,5-bis((trimethylsilyl)ethynyl)-1-methoxy-4-decyloxybenzene (4)
(5.14g, 10 mmol), THF (40 mL) and methanol (20 mL). The flask was capped and argon
was bubbled through the solution for 30 minutes. The reaction mixture was treated with an
oxygen-free 40% aqueous KOH solution (2 mL), stirred for 19 hours, and then poured into
hexanes (200 mL). The organic solution was washed with water (3 x 100 mL), and then
dried (MgSO4), and concentrated in vacuo. The resulting residue dissolved in hexanesCH 2Cl 2 (1:1) and filtered through a one inch plug of silica gel. The filtrate was once again
concentrated in vacuo, and the resulting solid recrystallized from hexanes to afford 5 as light
yellow needles (2.36 g, 67%).
1H
NMR (250 MHz, CDCl 3) 8 6.97 (s, 1H), 6.96 (s, 1H), 3.98
(t, J = 6.7 Hz, 2H), 3.86 (s, 3H), 3.39 (s, 1H), 3.35 (s, 1H), 1.81 (qn, J = 7.9 Hz, 2H), 1.53-
1.12 (br m, 14H), 0.88 (t, J = 6.9 Hz, 3H);
13C
NMR (125 MHz, CDCl 3 ) 8 154.31, 154.07,
117.95, 115.98, 113.37, 112.55, 82.55, 82.52, 79.70, 69.70, 56.35, 31.88, 29.54, 29.51, 29.30,
29.11, 25.87, 22.65, 14.08.
Polymer (6). A 25 mL Schlenk flask equipped with a stir bar was charged with 2,5-diiodo-4decyloxyanisole (3) (200 mg, 0.39 mmol, 1 eq.), 2,5-diethynyl-4-decyloxyanisole (5) (0.107
g, 0.34 mmol, 0.9 eq.), and copper(I)iodide (5.5 mg, 29 jlmol, 0.06 eq.). The flask was
placed under argon, and tetrakis(triphenylphosphine)palladium (0) (15 mg, 13 Jmol, 0.03
eq.) was added under a nitrogen atmosphere. Diisopropylamine (1.25 mL, 8.9 mmol, 23 eq.)
and toluene (3.5 mL) were successively added by syringe, and the mixture stirred at room
temperature for 30 minutes. The fluorescent yellow mixture was heated to 60 oC, stirred for
14 hours, and then cooled to room temperature. The resulting polymer was precipitated in
acetone (100 mL), filtered, and rinsed with hot ethanol and hexanes, to afford 6 as an
amorphous yellow solid (141 mg, 63%).
1H
NMR (300 MHz, CDC13 ) 8 7.05 (m, 2H), 4.05
(br m, 2H), 3.92 (m, 3H), 1.86 (m, 2H), 1.52 (m, 2H), 1.41-1.08 (br, 12H), 0.87 (t, J= 6.6
Hz, 3H);
13 C
NMR (125 MHz, CDC13 ) 8 (including low intensity peaks corresponding to end
groups) 153.92, 153.85, 153.72, 153.55, 117.52, 117.33, 115.5-115.1, 91.8-91.2, 69.78,
69.74, 69.68, 69.64, 56.52, 56.46, 56.39, 31.90, 29.69-29.57, 29.51-29.41, 29.40-29.28,
26.03, 26.01, 25.98, 25.95, 29.67, 14.09; GPC: Mw = 44,818; Mn = 13,940; PDI = 3.22
1-((6-Bromohexyl)oxy)-4-decyloxybenzene (8). A 500 mL three-necked round bottomed
flask equipped with a stir bar and condenser was charged with 1,6-dibromohexane (50 mL,
0.33 mol, 5 eq.), potassium carbonate (17.76 g, 0.13 mol, 2 eq.), and acetone (100 mL). The
reaction mixture was heated to reflux and a solution of p-decyloxyphenol (7) (14.92 g, 64
mmol, 1 eq.) in acetone (80 mL) was added dropwise at 10 mL/hr using a syringe-pump.
After 48 hours, the flask was cooled to room temperature, and the solution concentrated in
vacuo. The residue was dissolved in CHC13 (300 mL), washed sequentially with water (150
mL) and saturated aqueous NH 4 Cl (2 x 150 mL), and then dried (MgSO4), and concentrated
in vacuo. Ethanol was added to the residue to precipitate a white solid, which was filtered
and rinsed with more ethanol. After recrystallization (CHC13 -EtOH), 18.55 g (72%) of 8 was
obtained as large white plates.
1H
NMR (300 MHz, CDC13) 8 6.81 (s, 4H), 3.90 (m, 4H),
3.42 (t, J = 6.9 Hz, 2H), 1.89 (m, 2H), 1.75 (m, 4H), 1.55-1.15 (br m, 18H), 0.88 (t, J = 6.9
Hz, 3H);
13 C
NMR (125 MHz, CDCl 3) 8 153.19, 153.00, 115.30, 115.28, 68.55, 68.26,
33.75, 32.65, 31.86, 29.55, 29.53, 29.39, 29.36, 29.29, 29.17, 27.90, 26.02, 25.27, 22.65,
14.09.
1-((6-Bromohexyl)oxy)-4-decyloxy-2,5-diiodobenzene (9). A 100 mL round bottomed
flask equipped with a stir bar and a condenser was charged with 1-((6-bromohexyl)oxy)-4decyloxybenzene (8) (1.01 g, 2.4 mmol, 1 eq.), potassium iodate (0.22 g, 1.01 mmol, 0.40
eq.), and iodine (0.68 g, 2.68 mmol, 1.1 eq.). Glacial acetic acid (25 mL), conc. sulfuric acid
(0.25 mL), and water (2.5 mL) were added, and the mixture heated to reflux for 17 hours.
After cooling to room temperature, the excess iodine was quenched with 10% aqueous
Na2S 2 04. The mixture was diluted with CHC13 (100 mL) and the organic layer washed
sequentially with saturated aqueous NaHCO3 (3 x 50 mL) and saturated aqueous NaCl (50
mL), and then dried (MgSO4), and concentrated in vacuo. Flash chromatography (10%
CH 2 Cl2 /90% hexanes, Rf = 0.23) afforded 9 as a white solid (1.03 g, 63%), which contained
approximately 23% primary alkyl iodide.
1H
NMR (300 MHz, CDC13 ) 8 7.17 (s, 2H), 3.93
(m, 4H), 3.44 (t, J = 6.9 Hz, 2H), 3.22 (t, J = 6.9 Hz, iodide), 1.9-1.7 (br m, 6H), 1.6-1.4 (br
m, 6H), 1.4-1.2 (br m, 12H), 0.88 (t, J = 6.6 Hz, 3H);
13 C
NMR (125 MHz, CDC13 ) 8
152.72, 152.51, 122.56, 122.52, 86.25, 86.23, 70.14, 69.85, 33.57, 33.23 (iodo), 32.53, 31.76,
29.98 (iodo), 29.42, 29.40 (iodo), 29.18, 29.14, 29.02, 28.82, 27.67, 25.88, 25.14, 24.90,
22.55, 14.06.
1-((6-(Dimethylamino)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene
(11). A 100 mL three-
necked round bottomed flask equipped with a stir bar and a condenser was charged with 1((6-bromohexyl)oxy)-4-decyloxy-2,5-diiodobenzene (9) (7.0 g, 10 mmol, 1 eq.), diethyl ether
(20 mL), and dimethylhydrazine monohydrate (1.24 mL, 16 mmol, 1.55 eq.). The mixture
was heated to reflux, by which time a white solid (10) began to form. After cooling to room
temperature the solvent was decanted from the solid in the reaction flask, and the remaining
white solid rinsed with diethyl ether (4 x 50 mL). A 4N HCI (100 mL) solution was used to
rinse the solid into a 250 mL three-necked flask equipped with a stir bar and a condenser.
The flask was cooled to 0 oC in an ice bath, and a solution of NaNO2 (2.10 g, 30 mmol, 2.90
eq.) in water (10 mL) was added dropwise to the reaction mixture. After warming to room
temperature overnight, the flask was again cooled in ice, and a 50% aqueous NaOH solution
was added until the solution was strongly basic. The solution was washed with water (3 x 50
mL) and then dried (MgSO4), and concentrated in vacuo. Flash chromatography (90%
CH 2 C12/10% methanol, Rf = 0.47) afforded 11 (3.88 g, 59%) as a white solid.
1H NMR
(250
MHz, CDCl 3 ) 8 7.17 (s, 2H), 3.93 (t, J= 6.3 Hz, 4H), 2.28 (m, 8H), 1.80 (m, 4H), 1.53-1.20
(br m, 20H), 0.88 (t, J = 6.8 Hz, 3H);
13 C NMR
(125 MHz, CDC13) 8 152.76, 152.65,
122.66, 122.60, 86.23, 70.22, 70.07, 59.54, 45.24, 31.83, 29.48, 29.47, 29.51, 29.20, 29.05,
28.99, 27.30, 26.97, 25.94, 25.91, 22.62, 14.08.
Polymer (12). An oven-dried 25 mL Schlenk tube equipped with a stir bar was charged with
2,5-diethynyl-4-decyloxyanisole (5) (0.47 g, 151 lmol, 1 eq.) and placed under argon before
adding THF (1.5 mL) to dissolve the solid. The flask was cooled to 0 OC in an ice bath and
n-butyllithium (0.23 mL, 1.44 M in hexanes, 2.2 eq) was added via syringe to the solution,
causing it to turn to a blue-green mixture. After stirring for 30 minutes, tributyltin chloride
(0.10 mL, 369
mol, 2.4 eq.) was added to the solution, which caused it to turn a clear orange
color. A separate 25 mL Schlenk tube was equipped with a stir bar and charged with 1-((6(dimethylamino)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene (11) (0.089 g, 1.41 x
10
-4
mol,
0.95 eq.). The flask was placed under argon and tetrakis(triphenylphosphine)palladium (0) (5
mg, 4.33 jimol, 0.03 eq.) was added under a nitrogen atmosphere. Diisopropylamine (1.50
mL, 11 mmol, 71 eq.) and toluene (1 mL) were successively added by syringe, and then the
contents were transferred to the aforementioned flask via cannula. After 24 hours, a small
quantity of copper(I)iodide was added to the reaction mixture under argon flow. After a few
minutes the solution began to fluoresce a green color. The mixture was heated to 75 'C for
three hours, and then precipitated in rapidly stirring acetone (50 mL), filtered, and rinsed with
hot acetone, ethylenediamine, and finally hot hexanes. After drying under high vacuum, 0.12
g (117%) of 12 was obtained as an orange solid. 1H NMR (250 MHz, CDC13 ) 8 7.02 (m,
4H), 4.10-3.85 (br m, 7H), 2.22 (m, 8H), 1.87 (m, 6H), 1.6-1.05 (br m, 36H), 0.87 (br t, J=
6.8 Hz, 6H)
Polymer (13). Polymer (12) (11 mg, 15.4 pmol, 1 eq.), 1,3-propanesultone (2.1 mg, 17
gmol, 1.1 eq.), and THF (1.5 mL) were combined in a 3 mL round bottomed flask. After
stirring for 4 hours, the solution was concentrated in vacuo, to yield polymer (13), which was
not soluble.
1-((6-(Dimethylamino)hexyl)oxy)-4-decyloxy-2,5-bis(trimethylsilyl)ethynyl)benzene
(14). A 25 mL Schlenk flask equipped with a stir bar and was charged with 1-((6(dimethylamino)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene (11) (0.99 g, 1.57 mmol, 1 eq.),
trans-dichlorobis(triphenylphosphine)-palladium (II) (34 mg, 48 gmol, 0.03 eq.), and
copper(I)iodide (23 mg, 0.12 mmol, 0.06 eq.). The flask was placed under argon and then
diisopropylamine (2.0 mL, 0.014 mol, 2.5 eq.) and toluene (10 mL) were added successively
by syringe. (Trimethylsilyl)acetylene (0.5 mL, 3.5 mmol, 2.2 eq.) was added by syringe,
causing the solution to become a viscous, dark-brown mixture. Toluene (10 mL) was added
and the mixture stirred at room temperature for 48 hours. The reaction mixture was filtered
through a one inch plug of silica and eluted with CH 2 Cl 2 -MeOH (1:1). The filtrate was
concentrated in vacuo and the residue chromatographed (5% methanol/94% CH 2 C12 /1%
triethylamine) unsuccessfully. No product was obtained.
1-((6-(Phthalimido)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene
(15). 1-((6-
bromohexyl)oxy)-4-decyloxy-2,5-diiodobenzene (9) (0.46 g, 0.69 mmol, 1 eq.), potassium
phthalimide (0.18 g, 0.97 mmol, 1.25 eq.), hexadecyltributylphosphonium bromide (50 mg,
95 jtmol, 0.1 eq.), and toluene (2.5 mL) were combined in a 15 mL round bottomed flask.
The flask was equipped with a stir bar and a condenser, and heated to reflux for 24 hours.
After cooling to room temperature, the reaction mixture was filtered and the resulting solid
rinsed with diethyl ether. The filtrate was concentrated in vacuo to yield a yellow solid.
Flash chromatography (25% hexanes/75% CH 2C12 , Rf = 0.29) afforded 15 (0.49 g, 97%) as a
white solid.
1H
NMR (250 MHz, CDCl 3 ) 8 7.84 (m, 2H), 7.69 (m, 2H), 7.15 (s, 2H), 3.92 (t,
J= 6.3 Hz, 4H), 3.71 (t, J = 7.3 Hz, 2H), 1.79 (m, 6H), 1.56-1.20 (m, 18H), 0.88 (t, J= 6.8
Hz, 3H);
13 C
NMR (125 MHz, CDC13 ) 8 168.34, 152.74, 152.62, 133.76, 132.04, 123.07,
122.62, 122.57, 86.20, 70.22, 69.98, 37.85, 31.84, 29.49, 29.47, 29.25, 29.21, 29.06, 28.90,
28.48, 26.46, 25.95, 25.65, 22.63, 14.09.
1-((6-(Phthalimido)hexyl)oxy)-4-decyloxy-2,5-((trimethylsilyl)ethynyl)benzene
(16). A
25 mL Schlenk flask equipped with a stir bar was charged with 1-((6(phthalimido)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene (15) (0.39 g, 0.53 mmol, 1 eq.),
trans-dichlorobis(triphenylphosphine)palladium (II) (15 mg, 21.4 gmol, 0.03 eq.), and
copper(I)iodide (28 mg, 0.15 mmol, 0.10 eq.). The flask was placed under argon, and then
toluene (5 mL) and diisopropylamine (0.30 mL, 2.14 mmol, 3.0 eq.) were successively added
by syringe. The deep-red solution was treated with (trimethylsilyl)acetylene (0.20 mL, 1.42
mmol, 2.2 eq.), and stirred at room temperature for 24 hours. The black mixture was
concentrated in vacuo, and then filtered through a one inch plug of silica gel and eluted with
CH 2 C12 -MeOH (1:1). The solvent from the filtrate was once again evaporated to yield a
black solid. Flash chromatography (10% diethyl ether/90% petroleum ether, Rf = 0.16)
afforded 16 (0.32 g, 87%) as a light orange solid. 1H NMR (250 MHz, CDC13 ) 8 7.84 (m,
2H), 7.71 (m, 2H), 6.87 (s, 2H), 3.93 (m, 4H), 3.70 (t, J = 7.2 Hz, 2H), 1.9-1.65 (br m, 6H),
1.6-1.15 (br m, 18H), 0.88 (t, J = 6.9 Hz, 3H), 0.25 (m, 18H);
13 C
NMR (125 MHz, CDC13 )
8 168.35, 153.93, 153.79, 133.78, 132.08, 123.09, 117.04, 117.01, 113.82, 113.78, 100.95,
100.05, 69.32, 69.06, 37.89, 31.84, 29.59, 29.54, 29.38, 29.28, 29.11, 28.54, 26.60, 25.97,
25.56, 22.64, 14.09, -0.09.
1-((6-Aminohexyl)oxy)-4-decyloxy-2,5-diiodobenzene
(18). 1-((6-
(phthalimido)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene (15) (2.10 g, 2.87 mmol, 1 eq.),
hydrazine monohydrate (7.0 mL, 0.14 mol, 50 eq.), and 95% ethanol (125 mL) were
combined in a 250 mL round bottomed flask equipped with a stir bar and a condenser, and
the solution heated to reflux for 24 hours. After cooling to room temperature, the reaction
mixture was partitioned between diethyl ether (400 mL) and water (200 mL), and the organic
layer was washed with water (4 x 200 mL). The aqueous layers were collected and extracted
with diethyl ether (250 mL). The combined organic fractions were combined dried (K2 C0 3)
and concentrated in vacuo. Flash chromatography (10% methanol/89% CH 2C12/1%
triethylamine, Rf = 0.16) afforded 18 (1.59 g, 92%) as a white solid.
1H
NMR (300 MHz,
CDC13 ) 8 7.17 (s, 2H), 9.30 (m, 4H), 2.71 (t, J = 6.6 Hz, 2H), 1.82 (m, 4H), 1.56-1.21 (br m,
20H), 0.88 (t, J= 6.6 Hz, 3H);
13 C NMR
(125 MHz, CDCl 3) 8 152.75, 152.64, 122.61,
122.60, 86.22, 86.21, 70.22, 70.06, 41.98, 33.45, 31.83, 29.48, 29.47, 29.25, 29.20, 29.05,
29.02, 26.46, 25.95, 25.86, 22.62, 14.08.
1-((6-(Trifluoroacetamido)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene
(19). A flame-dried
25 mL round bottomed flask equipped with a stir bar was charged with 1-((6aminohexyl)oxy)-4-decyloxy-2,5-diiodobenzene (18) (0.18 g, 0.29 mmol, 1 eq.) and placed
under argon before adding CH 2 Cl 2 (10 mL) and pyridine (0.15 mL, 1.86 mmol, 6 eq.) to
dissolve the solid. The solution was cooled to -15 oC in a ice/NaCl bath, after which
trifluoroacetic anhydride (0.13 mL, 0.92 mmol, 3 eq.) was added via syringe, turning the
solution a gold color. The reaction mixture was warmed to room temperature over 90
minutes and then concentrated in vacuo to yield a golden, gummy residue. Flash
chromatography (15% EtOAc/85% hexanes, Rf = 0.25) afforded 19 (0.16 g, 78%) as a white
solid. 1H NMR (250 MHz, CDC13 ) 8 7.17 (s, 2H), 6.25 (br s, 1H), 3.93 (m, 4H), 3.39 (q, J=
6.7 Hz, 2H) 1.80 (m, 4H), 1.72-1.20 (br m, 20H), 0.88 (t, J= 6.9 Hz, 3H);
13 C
NMR (125
MHz, CDCl 3 ) 8 157.15 (J=36.6 Hz), 152.86, 152.56, 122.66, 122.62, 115.79 (J=288.0
Hz), 86.27, 86.17, 70.27, 69.90, 39.86, 31.85, 29.51, 29.50, 29.28, 29.23, 29.07, 28.86, 28.83,
26.29, 25.97, 25.67, 22.64, 14.10.
1-((6-(Trifluoroacetamido)hexyl)oxy)-4-decyloxy-2,5-((trimethylsilyl)ethynyl)benzene
(20). A 10 mL Schlenk flask equipped with a stir bar was charged with 1-((6(trifluoroacetamido)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene (19) (0.11 g, 0.16 mmol, 1
eq.), trans--dichlorobis(triphenylphosphine)palladium
(II) (4.1 mg, 5.84 plmol, 0.03 eq.), and
copper(I)iodide (2.6 mg, 0.14 mmol, 0.06 eq.). The flask was placed under argon, and then
toluene (5 mL) and diisopropylamine (0.20 mL, 2.14 mmol, 3.0 eq.) were successively added
via syringe. The deep-red solution was treated with (trimethylsilyl)acetylene (0.15 mL, 1.06
mmol, 2.2 eq.), and stirred at room temperature for 18 hours. The resulting black mixture
was filtered through a one inch plug of silica gel and eluted with ethyl acetate. The filtrate
was concentrated in vacuo to yield a black solid. Flash chromatography (10% EtOAc/90%
hexanes, Rf = 0.20) afforded 20 (90 mg, 91%) as a light brown solid.
1H
NMR (250 MHz,
CDC13 ) 8 6.88 (s, 2H), 6.25 (br s, 1H), 3.94 (m, 4H), 3.39 (q, J= 6.7 Hz, 2H), 1.75 (m, 4H),
1.65-1.15 (br m, 20H), 0.88 (t, J = 6.9 Hz, 3H), 0.25 (m, 18H);
13 C
NMR (125 MHz,
CDC13 ) 8 154.08, 153.71, 117.12, 117.11, 113.93, 113.79, 101.03, 100.91, 100.23, 100.04,
69.38, 68.99, 39.89, 31.88, 29.63, 29.59, 29.42, 29.33, 29.31, 29.04, 28.95, 26.38, 26.01,
25.59, 22.68, 14.12, -0.05, -0.07.
1-((6-Aminohexyl)oxy)-4-decyloxy-2,5-diethynylbenzene
(21). A 10 mL round bottomed
flask equipped with a stir bar was charged with 1-((6-(trifluoroacetamido)hexyl)oxy)-4decyloxy-2,5-((trimethylsilyl)ethynyl)benzene (20) (25 mg, 3.93 pmol, 1 eq.) and 5 mL
THF-methanol-H 2 0 (2:2:1). The flask was capped and argon was rapidly bubbled through
the solution for 10 minutes. Lithium hydroxide monohydrate (16 mg, 0.39 mmol, 10 eq.)
was added to the solution and the reaction mixture stirred at room temperature for 24 hours.
The solvent was removed in vacuo and the residue dissolved in CH 2C12 (50 mL). The
organic solution was then washed sequentially with saturated aqueous NH4 Cl (25 mL),
saturated aqueous NaHCO 3 (50 mL), and saturated aqueous NaCl (25 mL) and then
concentrated in vacuo. Flash chromatography (94% CH 2C12 /5% methanol/1% triethylamine,
Rf= 0.15) afforded 21 (14 mg, 91%) as a yellow solid.
1H
NMR (500 MHz, CDC13 ) 8 6.94
(m, 2H), 4.70 (br s 2H), 3.96 (m, 4H), 3.40(s, 1H), 3.33 (s, 1H), 2.85 (t, J = 7.0 Hz, 2H), 1.80
(m, 4H), 1.66 (m, 2H), 1.55-1.15 (br m, 18H), 0.88 (t, J = 7.0 Hz, 3H)
1-((6-(Dimethylphosphinoyl)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene
(22).
A flame-dried 50 mL Schlenk flask equipped with a stir bar was charged with NaH (0.11 g,
4.5 mmol, 3 eq.) and THF (20 mL) and cooled to 0 oC in an ice bath. Dimethyl phosphite
(0.50 mL, 5.45 mmol, 3.2 eq.) was added via syringe and the mixture was allowed to warm to
room temperature over 60 minutes. The clear solution was treated with 2-(1bromohexyloxy)-5-decyloxy-1,4-diiodobenzene (9) (1.00 g, 1.50 x mmol, 1 eq.) in THF (5
mL), and then stirred at room temperature for 24 hours in the absence of light. The flask was
heated to 50 OC for 11 hours, and then filtered through a one inch plug of silica using ethyl
acetate as the eluent. The filtrate was concentrated in vacuo to yield a white solid. Flash
chromatography (EtOAc, Rf = 0.30) followed by recrystallization (hexanes) afforded 22
(0.55 g, 77%) as a white fluffy solid.
1H
NMR (300 MHz, CDC13) 8 7.17 (s, 2H), 3.93 (t, J=
6.2 Hz, 4H), 3.74 (d, J = 10.6 Hz, 6H), 1.85-1.20 (br m, 26H), 0.88 (t, J = 6.5 Hz, 3H);
13 C
NMR (125 MHz, CDCl 3 ) 8 152.78, 152.59, 122.60, 122.59, 86.21, 86.16, 70.22, 69.93, 52.20
(d, J = 6.8 Hz), 31.83, 30.11 (d, J= 17.0 Hz), 29.48, 29.47, 29.25, 29.20, 29.05, 28.77, 25.94,
25.54, 24.52 (d, J = 140.5 Hz), 22.62, 22.20 (d, J = 5.03 Hz), 14.08.
1-((6-Bromohexyl)oxy)-4-decyloxy-2,5-((trimethylsilyl)ethynyl)benzene
(23). A 25 mL
Schlenk flask equipped with a stir bar was charged with 1-((6-bromohexyl)oxy)-4-decyloxy2,5-diiodobenzene (9) (0.5 g, 0.75 mmol, 1 eq.), trans-dichlorobis(triphenylphosphine)palladium (II) (16 mg, 23 jtmol, 0.03 eq.), and copper(I)iodide (9 mg, 47 gmol, 0.06 eq.).
The flask was placed under argon, and then toluene (10 mL) and diisopropylamine (0.40
mL, 2.8 mmol, 4.0 eq.) were successively added by syringe. The deep-red solution was
treated with (trimethylsilyl)acetylene (0.24 mL, 1.7 mmol, 2.2 eq.), and stirred at room
temperature for 24 hours. The black mixture was filtered through a one inch plug of silica
gel and eluted with CH 2C12 . Concentration of the filtrate in vacuo yielded a black oil. Flash
chromatography (30% CH 2 Cl 2/70% hexanes, Rf = 0.25) afforded 23 (0.44 g, 96%) as a light
yellow solid.
1H
NMR (250 MHz, CDCl 3 ) 8 6.89 (s, 2H), 3.94 (m, 4H), 3.42 (t, J= 6.8 Hz,
2H), 1.83 (m, 6H), 1.60-1.15 (br m, 20H), 0.88 (t, J= 6.8 Hz, 3H), 0.24 (m, 18H);
13 C
NMR
(125 MHz, CDC 3 ) 8 154.01, 153.75, 117.08, 113.87, 113.83, 100.97, 100.93, 100.10,
100.02, 69.33, 69.01, 33.70, 33.44 (iodo), 32.71, 31.85, 30.21 (iodo), 29.60, 29.55, 29.39,
29.29, 29.09, 27.89, 25.98, 25.19, 24.96 (iodo), 22.65, 14.10, 6.85 (iodo), -0.05, -0.09.
1-((6-(Dimethylphosphinoyl)hexyl)oxy)-4-decyloxy-2,5-((trimethylsilyl)ethynyl)benzene
(24). A flame-dried 50 mL Schlenk flask equipped with a stir bar was charged with NaH
(0.111 g, 4.64 mmol, 3 eq.) and THF (20 mL) and cooled to 0 oC in an ice bath. Dimethyl
phosphite (0.50 mL, 5.45 mmol, 3.2 eq.) was added via syringe and the mixture allowed to
warm to room temperature over 60 minutes. The clear solution was then treated with 1-((6bromohexyl)oxy)-4-decyloxy-2,5-((trimethylsilyl)ethynyl)benzene (23) (1.01g, 1.66 mmol, 1
eq.) in THF (5 mL) and then stirred at room temperature for 24 hours in the absence of light.
The flask was heated to 60 oC for 24 hours, and then filtered through a one inch plug of silica
using EtOAc-CH2Cl2 (1:1) as the eluent. The filtrate was concentrated in vacuo to afford 24
(0.80 g, 76%) as a light yellow solid. This product was used without further purification. 1H
NMR (250 MHz, CDC13 ) 8 6.88 (s, 2H), 3.94 (t, J = 6.3 Hz, 4H), 3.73 (d, J = 10.9 Hz, 6H),
1.85-1.20 (br m, 26H), 0.88 (t, J = 6.8 Hz, 3H), 0.25 (s, 18H);
13C
NMR (125 MHz, CDC13 )
8 153.92, 153.70, 116.98, 116.97, 113.79, 113.73, 100.91, 100.86, 100.03, 99.94, 69.25,
68.96, 52.11 (d, J = 6.4 Hz), 31.78, 30.20 (d, J= 17.0 Hz), 29.53, 29.48, 29.32, 29.22, 28.92,
25.91, 25.40, 24.56 (J = 140.5 Hz), 22.58, 22.22 (J = 5.0 Hz), 14.03, -0.15, -0.16.
1-((6-(Dimethylphosphinoyl)hexyl)oxy)-4-decyloxy-2,5-diethynylbenzene
(25). A 100
mL three-necked round bottomed flask equipped with a stir bar was charged with 1-((6(dimethylphosphinoyl)hexyl)oxy)-4-decyloxy-2,5-((trimethylsilyl)ethynyl)benzene
(24) (0.42
g, 0.66 mmol, 1 eq.), DMF (30 mL), water (0.15 mL) and methanol (0.30 mL). The flask
was capped and argon was rapidly bubbled through the solution for 20 minutes. Potassium
fluoride (0.123 g, 2.12 mmol, 3 eq.) was then added to the flask, and the solution stirred at
room temperature for 24 hours. The DMF was removed under high vacuum, and the
resulting pink residue dissolved in CHC13 and filtered. The solid was recrystallized
(CH2C12-hexanes) and chromatographed (EtOAc) to afford 25 (0.22 g, 67%) as a white solid.
1H NMR (300 MHz, CDCl 3 ) 6 6.94 (m, 2H), 3.97 (t, J = 6.9 Hz, 4H), 3.74 (d, J= 10.8 Hz,
6H), 3.33 (m, 2H), 1.85-1.20 (br m, 26H), 0.88 (t, J= 7.2 Hz, 3H);
13 C
NMR (125 MHz,
CDC13 ) 8 153.98, 153.78, 117.62, 117.60, 113.16, 113.17, 82.50, 82.46, 79.70, 79.69, 69.59,
69.30, 52.25 (d, J = 6.4 Hz), 31.89, 30.19 (d, J= 16.9 Hz), 29.55, 29.53, 29.31, 29.08, 28.79,
25.87, 25.42, 24.57 (d, J = 140.7 Hz), 22.67, 22.22 (d, J = 5.0 Hz), 14.12.
Polymer (26). A 10 mL Schlenk flask equipped with a stir bar was charged with 1-((6(dimethylphosphinoyl)hexyl)oxy)-4-decyloxy-2,5-diiodobenzene (22) (80 mg, 0.12 mmol, 1
eq.), 1-((6-(dimethylphosphinoyl)hexyl)oxy)-4-decyloxy-2,5-diethynylbenzene
(25) (0.58 g,
0.12 mmol, 1.03 eq.), and copper(I)iodide (1.5 mg, 7.88 gtmol, 0.07 eq.). The flask was
placed under argon, and tetrakis(triphenylphosphine)palladium (0) (12 mg, 10.4 gmol, 0.09
eq.) was added under a nitrogen atmosphere. Toluene (1.5 mL) and diisopropylamine (0.20
mL, 1.43 mmol, 12 eq.) were successively added by syringe, and the reaction mixture was
heated to 60 oC for 14 hours. After cooling to room temperature, CH 2 C12 -1,2dichlorobenzene (1:1) was added to dissolve the orange gel. The resulting viscous solution
was precipitated in hexanes (400 mL), filtered, and rinsed with hot hexanes to afford 26 as an
intractable amorphous solid. 1H NMR (250 MHz, CDC13 ) 8 8.55 (br s), 7.01 (br s), 4.04 (br
m), 3.75-3.45 (br m), 1.95-1.15 (br m), 0.88 (br t)
Triethylene glycol monomethyl ether p-toluenesulfonate (29). A 250 mL three-necked
round bottomed flask equipped with a stir bar and an addition funnel was charged with
triethylene glycol monomethyl ether (5.01 g, 31 mmol, 1 eq.), 4-dimethylaminopyridine (80
mg, 0.66 mmol, 0.02 eq.), CH 2 C12 (100 mL), triethylamine (8.75 mL, 62.8 mmol, 2 eq.), and
the cooled to -15 oC in an ice/NaCl bath. p-Toluenesulfonyl chloride (9.18 g, 48 mmol, 1.5
eq.) in CH 2C12 (75 mL) was added dropwise from the addition funnel to the reaction mixture
over 30 minutes, and then the flask was allowed to warm to room temperature overnight.
The brown solution washed sequentially with saturated aqueous NaHCO 3 (180 mL), 5%
aqueous HCI (200 mL), saturated aqueous NaHCO 3 (200 mL), and saturated aqueous NaCl
(200 mL) and then dried (MgSO 4 ), and concentrated in vacuo. Flash chromatography (15%
EtOAc/85% CH 2C12, Rf = 0.36) afforded 29 (8.64 g, 87%) as a light yellow oil.
1H
NMR
(250 MHz, CDC13 ) 8 7.80 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 4.16 (t, J = 4.9 Hz,
2H), 3.69 (t, J = 5.0 Hz, 2H), 3.95 (m, 6H), 3.53 (m, 2H), 3.37 (m, 3H), 2.45 (s, 3H);
13 C
NMR (125 MHz, CDC13) 6 144.62, 132.68, 129.62, 127.71, 71.62, 70.45, 70.26, 70.25,
69.07, 68.39, 58.75, 21.39.
1,4-Diiodo-3-decyloxyphenol
(30). A flame-dried 250 mL Schlenk flask equipped with a
stir bar was charged with 2,5-diiodo-4-decyloxyanisole (3) (10.08 g, 19.5 mmol, 1 eq.) and
then placed under argon. CH 2 C12 (100 mL) and trimethylsilyl iodide (3.0 mL, 21 mmol, 1.05
eq.) were successively added, causing the solution to turn light yellow. The flask was stirred
at room temperature for 4 days in the absence of light, and then methanol (10 mL) was added
to the quench the excess trimethylsilyl iodide. The reaction mixture was washed sequentially
with saturated aqueous NaCl (150 mL), saturated aqueous NaHCO 3 (150 mL), and saturated
aqueous NaCl (100 mL) and then dried (Na2SO4), and concentrated in vacuo. Flash
chromatography (50% hexanes/50% CH 2 C12 , Rf = 0.26) afforded 2.71 g of 30 in 46% yield
based on recovered 3 (4.05 g).
1H
NMR (250 MHz, CDC13) 8 7.41 (s, 1H), 7.02 (s, 1H),
3.91 (t, J = 6.4 Hz, 2H), 1.80 (qn, J = 6.6 Hz, 2H), 1.60-1.20 (br m, 14H), 0.88 (t, J= 6.8 Hz,
3H);
13 C
NMR (125 MHz, CDC13 ) 8 152.56, 149.70, 124.75, 120.82, 87.57, 84.39, 70.32,
31.88, 29.52, 29.51, 29.29, 29.25, 29.07, 25.99, 22.66, 14.13; MS (M + H) + found
501.98663, calc'd for C 16 H 2412 0 2 501.98658
1-((Triethylene glycol monomethyl ether)oxy)-4-decyloxy-2,5-diiodobenzene
(31). A 250
mL three-necked round bottomed flask equipped with a stir bar and a condenser was charged
with 1,4-diiodo-3-decyloxyphenol (30) (0.97 g, 1.93 mmol, 1 eq.), triethylene glycol
monomethyl ether p-toluenesulfonate (29) (0.69 g, 2.17 mmol, 1.1 eq.), potassium carbonate
(0.80 g, 5.80 mmol, 3 eq.), potassium iodide (31 mg, 0.18 mmol, 0.1 eq.), and acetone (100
mL). The mixture was heated at 75 'C for 48 hours, and then cooled to room temperature.
The solvent was removed in vacuo, and the residue partitioned between CH 2 C12 (250 mL)
and water (250 mL). The organic layer was separated, washed with saturated aqueous NaCl
(100 mL), and then dried (MgSO4), and concentrated in vacuo. Flash chromatography (35%
EtOAc/ 65% hexanes, Rf = 0.41) afforded 31 as a white solid (1.30 g, 90%).
1H
NMR (250
MHz, CDCl 3 ) 8 7.25 (s, 1H), 7.16 (s, 1H), 4.10 (m, 2H), 3.90 (m, 4H), 3.80 (m, 2H), 3.67 (m,
4H), 3.56 (m, 2H), 3.38 (s, 3H), 1.78 (qn, J = 6.5 Hz, 2H), 1.55-1.20 (br m, 14H), 0.88 (t, J=
6.8 Hz, 3H);
13 C NMR
(125 MHz, CDC13 ) 6 153.16, 152.67, 123.60, 122.52, 86.45, 86.18,
71.91, 71.09, 70.71, 71.55, 70.30, 70.24, 69.59, 59.01, 31.86, 29.51, 29.49, 29.27, 29.23,
29.07, 25.98, 22.64, 14.09.
1-((Triethylene glycol monomethyl ether)oxy)-4-decyloxy-2,5((trimethylsilyl)ethynyl)benzene (32). A 100 mL Schlenk flask equipped with a stir bar
was charged with 1-((triethylene glycol monomethyl ether)oxy)-4-decyloxy-2,5diiodobenzene (31) (0.60 g, 0.93 mmol, 1 eq.), trans-dichlorobis(triphenylphosphine)palladium (II) (19.2 mg, 27.4 gmol, 0.03 eq.), and copper(I)iodide (14.3 mg, 75.1 pgmol, 0.06
eq.). The flask was placed under argon, and then toluene (50 mL) and diisopropylamine
(0.60 mL, 4.28 mmol, 4.0 eq.) were successively added. The orange solution was treated
with (trimethylsilyl)acetylene (0.30 mL, 2.1 mmol, 2.2 eq.), and stirred at room temperature
for 48 hours. The black mixture was filtered through a one inch plug of silica gel and eluted
using ethyl acetate. The filtrate was removed in vacuo to yield a black oil that was
chromatographed (25% EtOAc/75% hexanes, Rf = 0.31) to afford 32 as a golden oil (0.47 g,
86%).
1H
NMR (300 MHz, CDC13) 8 6.92 (s, 1H), 6.88 (s, 1H), 4.12 (t, J= 5.1 Hz, 2H),
3.94 (t, J = 6.6 Hz, 2H), 3.87 (m, 2H), 3.79 (m, 2H), 3.66 (m, 4H), 3.54 (m, 2H), 3.37 (s, 3H),
1.76 (m, 2H), 1.48 (m, 2H), 1.40-1.20 (br m, 12H), 0.88 (t, J = 6.9 Hz, 3H), 0.26 (m, 18H);
13 C
NMR (125 MHz, CDCl 3 ) 8 154.32, 153.55, 117.76, 117.28, 114.16, 114.02, 101.02,
100.85, 100.23, 100.09, 71.92, 71.12, 70.75, 70.51, 69.69, 69.55, 69.41, 58.97, 31.84, 29.59,
29.54, 29.38, 29.30, 29.28, 25.98, 22.63, 14.06, -0.07, -0.10.
1-((Triethylene glycol monomethyl ether)oxy)-4-decyloxy-2,5-diethynylbenzene
(33). A
25 mL two-necked round bottomed flask was equipped with a stir bar and charged with 1((triethylene glycol monomethyl ether)oxy)-4-decyloxy-2,5-((trimethylsilyl)ethynyl)benzene
(32) (0.40 g, 0.676 mmol, 1 eq.) and methanol (15 mL). The flask was capped and argon
bubbled through the solution for 45 minutes. Tetrabutylammonium fluoride hydrate (0.48 g,
1.85 mmol, 2.4 eq.) was then added to the flask under argon and the mixture stirred at room
temperature for 2 hours. The red solution was then concentrated in vacuo and the residue
partitioned between CH 2C12 (100 mL) and water (50 mL). The organic layer was washed
with saturated aqueous NaCl (50 mL), and then dried (MgSO4), and concentrated in vacuo.
Flash chromatography (35% EtOAc/65% hexanes, Rf = 0.23) afforded 33 (0.27 g, 90%) as a
red solid.
1H
NMR (250 MHz, CDC13 ) 8 7.00 (s, 1H), 6.94 (s, 1H), 4.15 (t, J= 5.2 Hz, 2H),
3.97 (t, J = 6.6 Hz, 2H), 3.87 (m, 2H), 3.77 (m, 2H), 3.67 (m, 4H), 3.56 (m, 2H), 3.38 (s, 3H),
3.33 (s, 2H), 1.78 (qn, J = 7.8 Hz, 2H), 1.55-1.20 (br m, 14H), 0.88 (t, J = 6.8 Hz, 3H);
13 C
NMR (125 MHz, CDC13 ) 6 154.25, 153.63, 118.35, 117.50, 113.47, 113.20, 82.59, 82.52,
79.67, 79.55, 71.89, 71.00, 70.66, 70.51, 69.56, 69.54, 69.48, 58.97, 31.85, 29.50, 29.48,
29.27, 29.04, 25.83, 22.63, 14.07.
Polymer (34). A 10 mL Schlenk flask equipped with a stir bar was charged with 1((triethylene glycol monomethyl ether)oxy)-4-decyloxy-2,5-diiodobenzene (31) (73.1 mg,
0.11 mmol, 1 eq.), 1-((triethylene glycol monomethyl ether)oxy)-4-decyloxy-2,5diethynylbenzene (33) (51.6 g, 0.11 mmol, 1.03 eq.), and copper(I)iodide (3.9 mg, 20.5
gmol, 0.07 eq.). The flask was placed under argon, and tetrakis(triphenylphosphine)palladium (0) (8 mg, 6.92 plmol, 0.18 eq.) was added under a nitrogen atmosphere. Toluene
(3.0 mL) and diisopropylamine (1.25 mL, 8.91 mmol, 79 eq.), were successively added by
syringe, and the mixture stirred at room temperature for 30 minutes. As the mixture became
viscous, toluene (2 mL) was added, after which, the mixture was heated to 60 oC for 24
hours. The polymer solution was then precipitated in methanol, filtered, and rinsed with hot
methanol, giving polymer 34 as an amorphous orange solid (85 mg, 90%).
1H
NMR (300
MHz, CDC13 ) 8 7.54 (br m), 7.06 (s), 7.01 (s), 4.24 (br m), 4.04 (br m), 3.92 (br m), 3.78 (br
m), 3.62 (br m), 3.51 (br m), 3.35 (br s), 1.86 (br, m), 1.64 (br m), 1.50 (br m), 1.40-1.1 (br
m), 0.87 (t, J= 6.9 Hz); GPC (soluble portion): Mw = 693,530; Mn = 151,731; PDI = 4.57.
(2-(p-Toluenesulfonyl)methyleneoxy)-15-crown-5
(36). A 250 mL three-necked round
bottomed flask equipped with a stir bar and an addition funnel was charged with 2-
hydroxymethyl 15-crown-5 (1.11 g, 4.43 mmol, 1 eq.), 4-dimethylaminopyridine (13 mg,
0.11 mol, 0.02 eq.), CH 2Cl 2 (100 mL), triethylamine (1.50 mL, 11 mmol, 2 eq.), and then
cooled to -15 'C in an ice/NaCl bath. A solution of p-toluenesulfonyl chloride (1.33 g, 6.95
mmol, 1.5 eq.) in CH 2 C12 (75 mL) was then added dropwise from the addition funnel to the
reaction mixture over a period of 30 minutes. The reaction mixture was allowed to warm to
room temperature overnight while stirring, and then washed with 5% aqueous HCI (2 x 100
mL), dried (MgSO4), and concentrated in vacuo. Flash chromatography (95% EtOAc/5%
ethanol, Rf = 0.42 to 0.09 streak) afforded 36 (1.09 g, 61%) as a clear, viscous oil.
1H
NMR
(250 MHz, CDCl 3 ) 8 7.79 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.2 Hz, 2H), 4.20-3.95 (br m,
3H), 3.85-3.45 (br m, 18H), 2.45 (s, 3H);
13 C NMR
(125 MHz, CDC13 ) 8 144.49, 132.68,
129.54, 127.69, 76.75, 70.89, 70.53, 70.35, 70.23, 70.19, 70.14, 70.11, 70.02, 69.64, 65.90,
21.37.
1-(2-methyleneoxy-15-crown-5)-4-decyloxy-2,5-diiodobenzene (37). A 50 mL round
bottomed flask equipped with a stir bar and a condenser was charged with 1,4-diiodo-3decyloxyphenol (30) (0.98 g, 1.96 mmol, 1 eq.), (2-p-toluenesulfonyl)methyleneoxy)-15crown-5 (36) (0.87 g, 2.15 mmol, 1.1 eq.), potassium carbonate (0.82 g, 5.94 mmol, 3 eq.),
potassium iodide (33 mg, 0.201 mmol, 0.1 eq.), and acetone (25 mL). The mixture was
heated to reflux for 48 hours and then allowed to cool to room temperature. The reaction
mixture was partitioned between ethyl acetate (100 mL) and water (100 mL), and then the
organic layer washed with water (100 mL). Evaporation of the organic layer gave a viscous
brown oil, which was chromatographed (75% EtOAc/25% CH 2 C12 , Rf = 0.41 to 0.25, streak)
to afford 37 (1.30 g, 91%) as a light yellow, viscous oil that solidified upon standing.
1H
NMR (250 MHz, CDCl 3 ) 8 7.22 (s, 1H), 7.16(s, 1H), 4.10-3.80 (br m, 7H), 3.75-3.55 (br m,
16H), 1.80 (qn, J= 8.0 Hz, 2H), 1.55-1.20 (br m, 14H), 0.88 (t, J= 6.9 Hz, 3H);
13 C NMR
(125 MHz, CDCl 3) 8 152.96, 152.60, 122.70, 122.62, 86.22, 85.94, 77.93, 71.22, 70.87,
70.84 (br), 70.80, 70.78, 70.57, 70.52, 70.50, 70.44, 70.27, 31.83, 29.48, 29.47, 29.25, 29.20,
29.06, 25.95, 22.61, 14.07.
1-(2-methyleneoxy-15-crown-5)-4-decyloxy-2,5-bis((trimethylsilyl)ethynyl)benzene
(38).
A 10 mL Schlenk flask equipped with a stir bar was charged with 1-(2-methyleneoxy-15crown-5)-4-decyloxy-2,5-diiodobenzene (37) (0.30 g, 0.41 mmol, 1 eq.), trans-dichlorobis(triphenylphosphine)palladium (II) (9.1 mg, 13 pmol, 0.03 eq.), and copper(I)iodide (4.8 mg,
25 pmol, 0.06 eq.). The flask was placed under argon, and then toluene (7.50 mL) and
diisopropylamine (0.30 mL, 2.14 mmol, 4.0 eq.) were successively added via syringe. The
orange solution was treated with (trimethylsilyl)acetylene (0.20 mL, 1.42 mmol, 2.2 eq.), and
stirred at room temperature for 24 hours. The resulting black mixture was filtered through a
one inch plug of silica gel and eluted with ethyl acetate-ethanol (1:1). Concentration of the
filtrate in vacuo yielded a brown solid. Flash chromatography (75% CH 2C12 /25% EtOAc, Rf
= 0.29 to 0.11, streak) afforded 38 (0.22 g, 81%) as a light yellow viscous oil, that solidified
upon standing.
1H
NMR (250 MHz, CDC13 ) 8 6.91 (s, 1H), 6.89 (s, 1H), 4.05-3.55 (br m,
23H), 1.79 (qn, J= 8.2 Hz, 2H), 1.55-1.15 (br m, 14H), 0.88 (t, J= 6.9 Hz, 3H), 0.27 (m,
18H);
13 C
NMR (125 MHz, CDC13 ) 8 154.08, 153.58, 117.32, 116.86, 113.96, 113.69,
101.08, 100.87, 100.20, 99.85, 78.05, 73.42, 71.14, 71.12, 70.91, 70.84, 70.82, 70.59, 70.57,
70.52, 70.15, 69.40, 31.85, 29.59, 29.55, 29.39, 29.29, 25.98, 22.64, 14.08, -0.04, -0.09.
1-(2-methyleneoxy-15-crown-5)-4-decyloxy-2,5-diethynylbenzene
(39). A 25 mL two-
necked round bottomed flask equipped with a stir bar was charged with 1-(2-methyleneoxy15-crown-5)-4-decyloxy-2,5-bis((trimethylsilyl)ethynyl)benzene (38) (0.19 g, 0.28 mmol, 1
eq.) and methanol (15 mL). The flask was capped and argon was bubbled through the
solution for 15 minutes. Tetrabutylammonium fluoride hydrate (0.20 g, 0.77 mmol, 2.4 eq.)
was added under argon, and the reaction mixture stirred at room temperature for 2 hours.
The reaction mixture was concentrated in vacuo, to yield a brown oil, which was dissolved in
CH 2 Cl 2 (125 mL) and washed with water (2 x 125 mL). The organic layer was collected and
once again concentrated in vacuo. Flash chromatography (50% CH 2 C12/47% EtOAc/3%
ethanol, Rf = 0.35 to 0.18, streak) afforded 39 (0.13 g, 87%) as a light red oil.
1H
NMR (300
MHz, CDC13) 8 6.99 (s, 1H), 6.94 (s, 1H), 4.15-3.55 (br m, 23H), 3.33 (s, 1H), 3.31 (s, 1H),
1.78 (m, 2H), 1.50-1.20 (br m, 14H), 0.88 (t, J = 7.2 Hz, 3H)
Polymer (40). A 10 mL Schlenk flask equipped with a stir bar was charged with 1-(2methyleneoxy-15-crown-5)-4-decyloxy-2,5-diiodobenzene (37) (63 mg, 86.2 gmol, 1 eq.), 1(2-methyleneoxy-15-crown-5)-4-decyloxy-2,5-diethynylbenzene (39) (47 mg, 88.9 jimol,
1.03 eq.), and copper(I)iodide (2 mg, 10.5 glmol, 0.07 eq.). The flask was placed under
argon, and tetrakis(triphenylphosphine)palladium (0) (10 mg, 8.65 jimol, 0.10 eq.) was added
under a nitrogen atmosphere. Toluene (3.0 mL) and diisopropylamine (1.25 mL, 8.91 mmol,
103 eq.) were successively added by syringe, and the mixture stirred at 60 oC for 48 hours.
The resulting polymer solution was precipitated in methanol, and the polymer collected by
centrifuge. This afforded 40 as a yellow solid (40.7 mg, 47%).
1H
NMR (300 MHz, CDC13)
8 7.54 (br m), 7.00 (br m), 4.20-3.45 (br m), 1.84 (br m), 1.66 (br m), 1.55-1.15 (br m), 0.87
(t, J = 6.8 Hz); GPC: Mw = 16,137; Mn = 8,095; PDI = 1.99.
Polymer (41). A 10 mL Schlenk flask equipped with a stir bar was charged with 1-(2methyleneoxy-15-crown-5)-4-decyloxy-2,5-diiodobenzene
(37) (71 mg, 96 jimol, 1 eq.), 1-
((triethylene glycol monomethyl ether)oxy)-4-decyloxy-2,5-diethynylbenzene (33) (44 mg,
99.0 gmol, 1.03 eq.), and copper(I)iodide (3.5 mg, 18.4 gmol, 0.06 eq.). The flask was
placed under argon, and tetrakis(triphenylphosphine)palladium (0) (9 mg, 7.8 jlmol, 0.10 eq.)
was added under a nitrogen atmosphere. Toluene (4.0 mL) and diisopropylamine (1.50 mL,
11 mmol, 111 eq.) were successively added by syringe, and the mixture stirred at 60 OC for
15 hours. The dark-brown polymer was precipitated in acetone (200 mL), filtered, and rinsed
with hot acetone and hot hexanes. After drying under high vacuum, polymer 41 was
obtained as a rust-colored solid (only partially soluble), (71 mg, 80%).
1H
NMR (250 MHz,
CDCl 3 ) 6 7.00(br m), 4.20-3.45(br m), 3.34 (s), 1.85 (br m), 1.55-1.15 (br m), 0.87 (t)
Polymer (42). A 10 mL Schlenk flask equipped with a stir bar was charged with 1-(2methyleneoxy-15-crown-5)-4-decyloxy-2,5-diiodobenzene
(37) (64 mg, 86.5 pmol, 1 eq.),
2,5-diethynyl-4-decyloxyanisole (5) (27 mg, 85.8 gmol, 1.03 eq.), and copper(I)iodide (1.6
mg, 8.40 gmol, 0.06 eq.). The flask was placed under argon, and tetrakis(triphenylphosphine)palladium (0) (10 mg, 8.65 gmol, 0.06 eq.) was added under a nitrogen
atmosphere. Toluene (3.0 mL) and diisopropylamine (1.50 mL, 11 mmol, 111 eq.)were
successively added by syringe, and the mixture was stirred at 60 'C for 24 hours. The cooled
polymer solution was precipitated in methanol, filtered, and rinsed with hot methanol. After
drying under high vacuum, polymer 42 was obtained as a bright yellow powder (61 mg,
89%).
1H
NMR (250 MHz, CDC13 ) 8 7.55 (br m), 7.04 (br m), 4.20-3.50 (br m), 1.86 (br m),
1.51 (br m), 1.40-1.15 (br m), 0.87 (t, J = 6.9 Hz); GPC: Mw = 113,791; Mn = 32,905; PDI
= 3.46.
Fluorescence Measurements. A fluorescence cuvette was filled with 3.0 mL of 2.7 gM
solution of 42 in THF. 3 gL aliquots of a 0.2 M KPF 6 solution in CH 3 CN were added to the
polymer solution, and the cuvette shaken for 60 seconds. Following equilibration, the final
spectra were taken; equilibration was determined when the spectrum remained unchanged
with time.
(1) ConjugatedPolymers and Related Materials;Salaneck, W. R.; Lundstrom, I.; Ranby, B.,
Ed.; Oxford University Press: New York, 1993, pp 502.
(2) Patil, A. O.; Heeger, A. J.; Wudl, F. Chem. Rev. 1988, 88, 183-200.
(3) Heeger, A. J. In Conjugated Polymers: the Interconnectionof chemical and Electronic
Structure; Salaneck, W.R.; Lundstrom, I; Ranby, B., Ed.; Oxford University Press: New
York, 1993, pp 502.
(4) Hide, F.; Diaz-Garcia, M. A.; Schwartz, B.; Heeger, A. J. Acc. Chem. Res. 1997, 30, 430436.
(5) Burroughes, J. H.; Bradley, D. D. C.; Brown, A. R.; Marks, R. N.; Mackay, K.; Friend, R.
H.; Burns, P. L.; Holmes, A. B. Nature 1990, 347, 539-541.
(6) Silva, A. P. d.; Gunaratne, H. Q. N.; Gunnlaugsson, T.; Huxley, A. J. M.; McCoy, C. P.;
Rademacher, J. T.; Rice, T. E. Chem. Rev. 1997, 97, 1515-1566.
(7) Masilamani, D.; Lucas, M. E. In FluorescentChemosensorsforMonitoring Potassium in
Blood and across BiologicalMembranes; Masilamani, Czarnick, A. W., Ed.; American
Chemical Society: Washington, D. C., 1993; Vol. 538, pp 235.
(8) Gentry, S. J. Catalytic Devices; Edmonds, T. E., Ed.; Chapman and Hall: New York,
1988, pp 326.
(9) Marsella, M. J.; Newland, R. J.; Carroll, P. J.; Swager, T. M. J. Am. Chem. Soc. 1995,
117, 9842-9848.
(10) Swager, T. M.; Marsella, M. J. Adv. Mater. 1994, 6, 595-597.
(11) Zhou, Q.; Swager, T. M. J. Am. Chem. Soc. 1995, 117, 12593-12602.
(12) Collings, P. J.; Hird, M. Introduction to Liquid Crystals; Taylor & Francis Ltd.: London,
1997.
(13) Collings, P. J. Nature's Delicate Phase of Matter; Princeton University Press: Princeton,
1990.
(14) Carr, N. In Polymeric Langmuir-Blodgettfilms;Chilton, J. A.; Chapman & Hall:
London, 1995, pp 351.
(15) Ros, M. B. In Other PhysicalPropertiesand PossibleApplications of Metallomesogens;
Serrano, J. L., Ed.; VCH Publishers: New York, 1996, pp 498.
(16) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tet. Lett. 1975, 50, 4467.
(17) Takahashi, S.; Kuroyama, Y.; Sonogashira, K.; Hagihara, N. Synthesis 1980, 627.
(18) Hegedus, L. S. Transition Metals in the Synthesis of Complex Organic Molecules;
University Science Books: Mill Valley, 1994.
(19) Swager, T. M.; Gil, C. J.; Wrighton, M. S. J. Phys. Chem. 1995, 99, 4886-4893.
(20) Serrette, A. ; Serrette, A., Ed.; University of Pennsylvania, 1994.
(21) Smith, R. F.; Coffman, K. J. Synth. Commun. 1982, 12, 801.
(22) Gibson, M. S.; Bradshaw, R. W. Angew. Chem. Int. Ed. Engl. 1968, 7, 919-930.
(23) Landini, D.; Rolla, F. Synthesis 1976, 389.
(24) Osby, J. O.; Martin, M. G.; Ganem, B. Tet. Lett. 1984, 25, 2093-2096.
(25) Muller, R. K.; Joos, R.; Felix, D.; Schreiber, J.; Wintner, C.; Eschenmoser, A. ; Muller,
R. K.; Joos, R.; Felix, D.; Schreiber, J.; Wintner, C.; Eschenmoser, A., Ed., pp 56-61.
(26) Kocienski, P. J. Protecting Groups; Georg Thieme Verlag: Stuttgart, 1994.
(27) Morita, T.; Okamoto, Y.; Sakurai, H. Tet. Lett. 1978, 2523-2526.
(28) Blackburn, G. M.; Ingleson, D. J.C.S. Perkin 1 1979, 1150-1153.
(29) Harvey, R. G.; Myers, T. C.; Jacobson, H. I.; Jensen, E. V. J. Am. Chem. Soc. 1957, 79,
2612-2615.
(30) Brana, M. F.; Moran, M.; Vega, M. J. P. d.; Pita-Romero, I. J. Org. Chem. 1996, 61,
1369-1374.
(31) LB films and measurements on LB films were done by Jinsang Kim.
(32) Gokel Crown Ethers & Cryptands; The Royal Society of Chemistry: Cambridge, 1994;
Vol. 3.
Appendix
NMR Spectra of Compounds
OCH 3
OC 10 H 2 1
9
8
7
6
5
Figure A1.1. 'H NMR spectrum (300 MHz, CDC13 ) of compound 2
4
3
1
0
OCH 3
OC1nF
.. ........
18i
r r
A 160.
_
__
8I
. . . . . ..14.
Figure A 1.2. 13C NMR spectrum (125 MHz, CDC13) of compound 2.
_ _
_ _
__
~
. . . . . -. . -. . .T. . . -.l. . 1
pp.
I
OCH 3
I
OC
.
S
I
.
I
9.5
10 H21
.
.
. I
9.0
.
.
. I
8.5
.
8I
8.0
~~I
.
7.5
7.0
6.5
6.0
5.5
5.0
4.5
PPM
Figure A1.3. 1H NMR spectrum (250 MHz, CDC13 ) of compound 3.
4.0
3.5
3.0
2.5
2.0
1.5
1.0
.5
0.0
OCH 3
I
OG 10H21
1 14
13
iso
3
Figure A1.4. 1 C NMR spectrum (125 MHz, CDC13) of compound 3.
g
00
40
30
pP
TMS'
i~--_
~
S5
9.0
mF8.5
O
7.5
7.0
6 5
6 0
55
5.0
mn-m-m-- 4.5
PPound 4.
Figure A1.5. 13C NMR spectrum (250 MHz, CDC13) of compound 4.
40
T 1
3 5
I Il I . I . .
3.0
2.5
r1
2 0
,.
1 5
JlT
10
I l l If l l Il F . . ..
.5
00
-.
.
TMS
N
OC 10 H 21
1IN
140
if
IN
0
Figure A1.6. 13 C NMR spectrum (125 MHz, CDC1 3) of compound 4.
M
40
0
pp.
OCH 3
OC 10 H21
9.5
5
'i.O
Figure A1.7.
1H
80
7 5
7 (
6 5
6.0
55
5.(0
f iM
415
NMR spectrum (250 MHz, CDC13 ) of compound 5.
4.0
35
0
.5
.0
1.5
10
5
00
OCH 3
OC01 H21
LIIVI
LII*~L
I1
I
I .
110
LI
LILI
P
MEWTWWW" 11VP
1
141
LN
IN
Figure A1.8. 13C NMR spectrum (125 MHz, CDC13 ) of compound 5.
4.
1~((11(~(mr(~l(l
OCH 3
\
n
C 10 H2 1
S4
Figure A1.9. 'H NMR spectrum (300 MHz, CDC13 ) of compound 6.
3
1
4
p
OCH 3
n
C 10H21
1.....1.~. .r.........llr~l. ...I.
18
140
Figure A1.10. 13C NMR spectrum (125 MHz, CDC13) of compound 6.
..L
L.
pPO
O(CH 2 ) 6 Br
OC loH 2 1
9
Figure A1.11.
8
7
6
)
of
compound
8.
'H NMR spectrum (300 MHz, CDC13 ) of compound 8.
4
O(CH 2 ) 6 Br
OC
10H21
00
Figure
3C
A1.12.
NMR
spectrum
(125
MHz,
CDC)
of
compound
8.
Figure Al.12. 13C NMR spectrum (125 MHz, CDC13) of compound 8.
4
.
O(CH 2) 6Br
I
I
OC 10H2 1
__
~ I_
~II,
0
Figure A1.13. 'H NMR spectrum (300 MHz, CDC13 ) of compound 9.
Ppm
O(CH 2 ) 6 Br
I
I
OC 10 H 2 1
----I-----'
----I---- ----LI--Y136
u
- --L--166
--L- -.140
_. ~.L~J~._ ~~~
. -_- ~._..-. --
. .-__.l_-L -l-- _L_____.JL _ __.. ---I--- ----L_I_-_.~
~_lYI~
16
a m3
Figure A1.14. 13C NMR spectrum (125 MHz, CDC13) of compound 9.
3
4l
aLi
j-J
4
I
I
OC
10 H2 1
'0
OO
9.5
9.0
8.5
e 0
7.5
7.0
65
6.0
5.5
5.0
4.5
4.0
PPM
Figure A1.15. 13C NMR spectrum (250 MHz, CDC13) of compound 11.
3.5
3.0
2.5
2.0
1.5
10
5
0.0
O N'
H21
OC
1OH
21
oo
00
e
160s
1
Figure Al.16.
13C
140
120
198
NMR spectrum (125 MHz, CDCI 3) of compound 11.
8o
6
40
20
pp.
0
3
OCH 3
CH2n
ClOH210
I-
I
C In H21
rT-TT-
9.5
r-i-r-r-r9.0
Figure Al.17.
-rT-r6.5
1H
-8.0
rr-r-7.5
---7.0
r
I.
6.5
I r, ,
G,
I
5.5
-r-T-T-rr TT-
rrr5.0
PPM
4.5
NMR spectrum (250 MHz, CDC13 ) of compound 12.
..O
-i I
3.5
r T-I
3.0
T
Frr-r2.5
I
2.0
....
I .
1.5
--rT-t1.0
i--rT--r.5
0.0
r-rrT-r
OC 10H21
00
9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
PPM
Figure A1.18.
1H
NMR spectrum (250 MHz, CDC13 ) of compound 15.
3.5
3.0
2.5
2.0
1.5
1.0
5
0.0
Ph
O- ,3
18
th
168
Figure A1.19. 13C NMR spectrum (125 MHz, CDC13) of compound 15.
TMS
-
OC
3L -llL
10 H2 1
TMS
Figure A1.20. 'H NMR spectrum (300 MHz, CDC13 ) of compound 16.
TMS
0 3
Phth
OC 10 H21 TMS
CI
18
16
140
12
16
8
Figure A1.21. 13 C NMR spectrum (125 MHz, CDC1 3) of compound 16.
SO
46
26
6
pp.
9
Figure A1.22.
8
1H
7
6
5
NMR spectrum (300 MHz, CDC13 ) of compound 18.
4
3
2
1
0
pP~
188
168
148
128
Figure A1.23. 13C NMR spectrum (125 MHz, CDC13) of compound 18.
pp.
H
O>
OC
CF3
rN
10 H 21
OC10H21
LLL
---~-~~-
1IIII
l
9.5
ll 1
9.0
lI
IV}li I
8.5
I
8.0
-ll
lI
7.5
III
7.0
I
6.5
1111
lll
111T--11
6.0
I
5.5
T
I
5.0
I
I
PPM
I
4.5
III
I
4.0
Figure A1.24. 'H NMR spectrum (250 MHz, CDC13 ) of compound 19.
II
.I
I
3.5
.
....................
I
3.0
2.5
2.0
1.5
1.0
.5
0.0
H
CF3
3N
I
O
OC 10 H 21
18
160
140
120
100
Figure A 1.25. 13C NMR spectrum (125 MHz, CDC13 ) of compound 19.
8
6
48
20
pp.
,CF
3
'TMS
1|1
1.
1
l .. i
i
9.5
.
11
.
9.0
Figure A1.26.
1
1.
. .1 1
l1
.1
. 11
. |1
. 1 1,
. 1l 1. .
8.5
8.0
7.5
1H
.1 .
7.0
1.
.
.1 . .
6.5
1..
6.0
I I
m ,
l
5.5
l
.
I.
I
5.0
.
. . .
. . I..
4.5
PPM
.
II
4.0
NMR spectrum (250 MHz, CDC1 3 ) of compound 20.
.
. . . . . . . . . . . . . . .
I I
3.5
III II
3.0
I1' '
2.5
. .
'1'11 1 1
2.0
1.5
17
1.0
1 1 f 1I
'77
I I
I
.5
0.0
'
.AIll
l.LbJLL
lJ-1
. |L
' ' ' ' ~-
.--
_U --.AL,. L.
.
I. _J A. I .
. 1.
L
...
..... .
t..
... LJ.I , .
.
,I.,. ....
.
.J
-~rrur~lrr-------------LuumlyYI~Y
~Wuur
-------------. . . . . ~~~~~~~~~~~~-~-~----
. .
1....1..
1480
Figure A1.27. 13C NMR spectrum (125 MHz, CDCI 3 ) of compound 20.
W..A&A6
.&i.h&&
.
e
ppl
o(-
OC
NH 2
10 H 21
-"r
6
3
?
6
s
4.36
4
9.37
0.39
Figure A1.28. 1H NMR spectrum (500 MHz, CDC13 ) of compound 21.
.
3
6.41
4.83
1.26
2L
4.2?
9.63
6.83 4.3
1
-
49.25
82.12
8.14
6
pp
O
O.
0
3 "OCH3
3
OCH3
IOC 10H21
0
7
l
43
Figure A1.29. 1H NMR spectrum (300 MHz, CDC1 3 ) of compound 22.
2
1
0 PPM
0
O.,-OCH3
I-o
CH3
OC 1 0H2 1
I
. .-.
18
120e
Figure A1.30. 13C NMR spectrum (125 MHz, CDC13) of compound 22.
so
I
I.....,,..
PP.
TMS
OC 10 H 2 1 TMS
90
5
6
.
7.0
5
60
55
5 0
4.5
4.0
Figure A1.31. 1H NMR spectrum (250 MHz, CDC1 3 ) of compound 23.
V
3.0
2.5
u
I
Ic
0.0
TMS
O-
Br
3
OC 10 H21 TMS
le9
lee
8e
Figure A1.32. 13C NMR spectrum (125 MHz, CDCl 3 ) of compound 23.
60
0
ppa
TMS.
9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
PPM
4.0
Figure A1.33. 'H NMR spectrum (250 MHz, CDC13 ) of compound 24.
3.5
3.0
2.5
2.0
1.5
1.0
.5
0.0
O
3-ppOCH3
TMS
O31 OCH 3
OC1 0 H21 TMS
IIL~
-III_
-I
~L
Lfl--llln._L LI-L~r
-rYI1-L
r rhllJY
L~ILU
* -Y- '~
L--W-LILII--.WYLLIU
ul.l.L*
WLrulWI~~~L~.
rY-rY~-LIU~-__L
-LI~~~- ~IY~~I)I~r\llll
-( l~l
l-rl
as
Figure
A1.34.
Figure A1.34.
13C
NMR spectrum (125 MHz, CDC13) of compound 24.
--.L
-Y
I
L
YLr
_L
-r 'L~~UII
0
8
PP.
pp.-
OCH 3
r----q
-~
21-T--r--T--rF Th
r; -r
7
1
1T
--
I-T
r--- -q- 77
1 - --
c'
Figure A1.35.
1H
NMR spectrum (300 MHz, CDC13 ) of compound 25.
1
rJFFM~
0
O
-
OCH 3
9"' 3 OCH 3
0
OC 1 H2 1
Y~,~
.- J.I Y~.,U .I- _-L--L-* * L Llk
.
180
18
Figure A1.36. 13 C NMR spectrum (125 MHz, CDC1 3) of compound 25.
8
.
..
.
.
..
.
LL
.
I. I
.:'IIIYIL1l.:_lIl
II
. ...
PP.
9.5
9.0
Figure A1.37.
8.5
1H
8.0
7.5
7.0
6.5
I
6.0
5.5
5.0
I .I
PPM
1
4.5
4.0
NMR spectrum (250 MHz, CDC13 ) of compound 26.
3.5
3.0
2.5
2.0
1.5
1.0
.5
TsO
O
9.5
O
9.0
Figure A1.38.
OCH 3
8.5
1H
8.0
7.5
70
65
60
7.0
6.5
6.0
I55
I
5.5
I
50
I
5.0
4.5
4.0
NMR spectrum (250 MHz, CDC13 ) of compound 29.
?.5
3.0
2.5
2.0
1.5
1.0
.5
0,0
TsO
O
O
18O
OCH3
160
146
180
10ee
Figure A1.39. 13 C NMR spectrum (125 MHz, CDC13 ) of compound 29.
S
6e
41
20
pp.
OH
Q--
OC loH 2 1
9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
PPM
Figure A1.40.
1H
NMR spectrum (250 MHz, CDC13 ) of compound 30.
3.5
3.0
2.5
2.0
1.5
1.0
.5
0.0
18
140
Figure A1.41. 13C NMR spectrum (125 MHz, CDC13) of compound 30.
0
O
0
OCH 3
OC 10 H 2 1
''
9.5
9.0
8.5
8.0
7.5
" """"''''''
'.0
7.0
.5
6.5
6.0I
6.0
'"'~
5.5
'
'----~-------------
5.0
4.5
PPH
4.0
Figure A1.42. 'H NMR spectrum (250 MHz, CDC13 ) of compound 31.
-------------3.5
3.0
2.5
2.0
-----------1.5
1.0
.5
0.0
0
0
0
OCH 3
...
.. -i
180
160
140
120
100
Figure A1.43. 13C NMR spectrum (125 MHz, CDC13) of compound 31.
80
60
40
20
ppm
MS
0
0
OC10 H2 1
~ 1 11r1
0
OCH 3
TMS
4
1 I I I I I I T I 1 I I I Il
9
B
7
1 I I I I I I I 1I Il
I
6
5
Figure A1.44. 'H NMR spectrum (300 MHz, CDC13 ) of compound 32.
.
II. II. II II' I I I I
,111,1
i 1 I- 1 r 1
1
1
0
r
ppm
TMS
O
O
OC InH I
LY"-T
--
P-1-M-9-T-rI-r-T*_LL*lrrLy
0
OCH 3
TMS
1- rc(/JI(I(YYI1Jrr
lee
Figure A1.45.
13 C NMR
-
148
YL.YILLYIYLLYL.
IYYU
lee
spectrum (125 MHz, CDC13) of compound 32.
OL
YIII((CIYMW
/r,
as
C
PP.
0
0
0
OCH 3
0C 10H2 1
I
I..I
I
9.5
..
I
9.0
....
I
8.5
i II IIIIIII
I...
8.0
7.5
7.0
6.5
IIIIII'1
6.0
5.5
IIII1
II
5.0
II1I' II1 IIIIIIIII1
4.5
4.0
PPM
Figure A1.46.
1H
NMR spectrum (250 MHz, CDC13 ) of compound 33.
3.5
3.0
III I
2.5
1
2.0
1.5
1.0
.5
0.0
O
0
0
OCH 3
OC 10 H 21
''"'~~~"--' -''Y--.."-'-"'~'.~-"-LI
_
-LII~I
--"T--Y1 I
l
1J
t
l l
l l
t l ,
1.
r 1,.1 1.
1r
180
Figure A1.47.
160
13C
1
1
-_-IL-I- _.YL.L 1~
- .L-.L
)L~
-Y~.___~ L-_LI~
_ ____I_-4_1-r-- -L *I
I ~-rr-L
i
l v
t
140
t
,
rI , t
lr
120
,
I~ylr'~ ----YI~
L
.
100
NMR spectrum (125 MHz, CDC1 3) of compound 33.
IL_.
YL~- - __ Y -I L~1
. .
40
. .
. . . .
. . ..
20
I I
20
I r
pm
IDm
'";
O
O
0
OCH 3
n
C10H21
9
8
7
6
5
Figure A1.48. 1H NMR spectrum (300 MHz, CDC13 ) of compound 34.
4
3
2
10
PPM
Tso
o)
9.5
9.0
8.5
8.0
7.5
7.0
4.0
3.5
3.0
2.5
.
Figure A1.49. 'H NMR spectrum (250 MHz, CDC13 ) of compound 36.
2.0
1.5
,71
1.0
.SV
.5
so
TsO
-
--
_-- -
...
,
180
-
P-I ....0
_
"
ME-r .
14
- -
A" 4
" -
r Ir-l
"
.W .
1
"
. -
11
-
----
-_
_ ...
-1
It--.ho-- -
- --
-
"
-
'--_
160
Figure A1.50. 13C NMR spectrum (125 MHz, CDC13 ) of compound 36.
-
7--
J
I*----LL~-_--~~r~-J
-
-r
,' ,
- ~.....~L1
- --r
---- -
-~r _~~r-L
rr.-r-
_l---.. .r
...........................
40
20
ppm
O
O
OC 1 0H 2 1
Cl
9.5
9.0
Figure A1.51.
8.5
1H
8.0
7.5
7.0
6.5
6.0
5.5
5.0
PPM
4.5
NMR spectrum (250 MHz, CDC13 ) of compound 37.
4.0
3.5
3.0
2.5
2.0
1.5
1.0
.5
0.0
0
"I
10H21
---~-~
--------~
~ -~
--~~------ ~~~~~--r
...00.WI.
i. . . . . . . . . I
182
lee
140
Figure A 1.52. 13C NMR spectrum (125 MHz, CDC13 ) of compound 37.
TMS
O
0
KOC10 H21
9.5
9.0
8.5
TMS
8.0
7.5
7.0
6.5
6.0
5.5
5.0
PPM
4.5
4.0
Figure A1.53. 1H NMR spectrum (250 MHz, CDC13 ) of compound 38.
3.5
3.0
2.5
2.0
1.5
1.0
.5
0.0
TMS
O
02
OC1H21
O
TMS
I.LI....... I.ITI
... . *.#. .l, l L - .I 41 1,
Y"W "YYY'
r'"r'
IIYYY- "a
160
180
Figure A1.54.
-AA-IY
I U(IY
13C
Y
140
I~HIIYLII
i20
. I,I .. .. *
11
LL~
i 00
E3(0
NMR spectrum (125 MHz, CDC13 ) of compound 38.
60
40
20
0
ppni
o
OC 10 H2 1
Jj
F-T-71
10
II I
I I I
9
I I i rI
l I r I I I
8
i
7
SL
I
j
I
i
6
Ti
T -T T
7
r-
i-F-
5
0.
0.029
Figure A1.55. 1H NMR spectrum (300 MHz, CDC13 ) of compound 39.
m-TT l-7-T- I I II
4
____L _J
3. 755
3
J
0 04:
TTF
mlT
l
2
[
1
LLL
0 03
0.079
0.409
0.064
mIT-TT-T1
I--r----
0 PPI
)
0o
O
_
\/
0O
-)n
C10H2 1
m
I
9
8
I
j
7
I
I
I
I
I
I
I
6
I
I
I
I
I
I
I
I
I
j
I
I
I
I
I
I I
5
Figure A1.56. 1H NMR spectrum (300 MHz, CDC1 3 ) of compound 40.
I
I
4
i
7I
I
i I I
3
t
I I
i II i
2
Ii
II I
0I PiP IM
0 PPM
9.5
9.0
8.5
8.0
7.5
7.0
6.5
6.0
5.5
5.0
PPM
4.5
4.0
Figure A1.57. 'H NMR spectrum (250 MHz, CDC13 ) of compound 41.
3.5
3.0
3.0
2.5 .
2.5
2.0i
2.0
1.5
.5
.0
1.0
.
.5
.5
0.0
I
0.0
OCH 3
0
4
n
Cl0H21
C10H21
.Ir--l- -----r. LL-~-- -.rrL-.- l. L_- L-.---L~~Yy r-I-~Y
0
Figure A1.58. 1H NMR spectrum (300 MHz, CDC13 ) of compound 42.
pp.